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By R. W. Snyder, H. J. Ramey

This paper presents the results of applying the Buckley-Leverett' displacement theory to petroleum reservoirs consisting of a finite number of layers. The layers are assumed to communicate only in the wellbores, and the reservoir may be represented as a linear system. Most previous investigations of this nature were limited by assumptions and by inconsistent calculation techniques. This study improves on previous work by applying the Buckley-Lev-erett displacement theory to a noncommunicating layered system where permeability, porosity, initial saturation, residual saturation and relative permeability vary from layer to layer in a logical and consistent manner. Gravity and capillary-pressure effects are neglected. A modification of the Higgins-Leighton calculation method was used in this study. Waterflood predictions were made with all properties varying, and then with only permeability varying using several inability ratios. These results were compared with the Stiles and Dykstra-Parsons predictions. It is shown that the latter methods generally give poor values for the breakthrough recovery and pessimistic predictions for the performance after breakthrough. Similar results were obtained for a gas-displacement case. lNTRODUCTION Field experience with immiscible displacement usually shows constant producing conditions until breakthrough of the displacing fluid. Then oil production continues at increasing displacing-to-displaced fluid ratios until the economic limit is reached. Three different ideal mechanisms are known that will produce this behavior: (1) relative permeability effects as described by Buckley-Leverett frontal advance theory,' (2) vertical stratification as considered by Stiles,2 Dykstra and Parsons5 and others and (3) different path lengths involved in areal (two-dimensional) flow between wells as described by Dyes et al.4 Without question, a combination of these factors modified by formation heterogeneity and other known and unknown factors actually does control the behavior of real systems. This paper presents results of an investigation of certain factors that should affect performance but which have received little attention to date. In 1944, Law5 demonstrated that porosity and perme- ability are often found to have normal and logarithmic-normal distributions, respectively. throughout cored intervals in natural formations. This led to the concept of the noncommunicating, multilayered reservoir model for immiscible displacement. This model assumes that the reservoir is composed of a number of layers that communicate only at the wellbores. Each layer is individually homogeneous, but may be different from every other layer. Stiles' presented one of the earliest applications of this model to waterflood performance. In addition, Stiles assumed that the initial saturations and relative permeabilities were the same for each layer, porosity was the same. displacement was piston-like, fluids were incompressible and injection into each layer was proportional to that layer's permeability capacity (permeability-thickness product). The last assumption would be true if the mobility ratio for the displacement were unity.21 Dykstra and Parsons" used the same model as Stiles, but rigorously included mobility ratios other than unity for piston-like displacement. Dykstra and Parsons used their general result to produce charts for log-normal permeability distributions between layers. Similarly, Muskat6 Pub1ished analytical solutions for linear and exponential permeability distributions. In 1959, Roberts' described a scheme for calculating water-drive performance for the noncommunicating, layered reservoir model which considered two-phase flow in the displaced region. Roberts used the same model and assumed that the injection rate into a layer was proportional to that layer's permeability capacity, but that flood front locations could be evaluated from the Dykstra-Parsons results. These assumptions are inconsistent, and a material balance cannot be maintained except for a mobility ratio of unity. At the same time, Kufus and Lynch8 coupled Buckley-Leverett displacement theory with the layered model to provide an improvement of the Dykstra-Parsons method that was consistent. In 1960, Higgins and Leighton9 resented a numerical method for calculating waterflood performance also considering two-phase flow in the displaced region. The result was used to investigate variation in absolute permeability and oil viscosity. An excellent, detailed history of using the noncomrnunicating, layered reservoir model was presented by Nielsen.'" The preceding techniques (and many related ones) were similar in that differences in initial saturations, residual saturations and relative permeabilities from layer to layer were neglected. It is well known that the irreducible water saturation is an important function of absolute permeability. Calhoun11 showed that the irreducible water saturation

By T. D. Yensen

AGING is a term that connotes a slow change in properties under ordinary operating conditions. It can be accelerated by increasing the temperature and by mechanical straining. The magnetic properties of iron and some of its alloys have for many years been known to be subject to such a change. But the cause of the change was not recognized until a few years ago after mechanical age-hardening in non-ferrous alloys of the "duralumin" type had been definitely shown, by means of solid solubility curves, changes in electrical resistance and microanalysis, to be caused by slow precipitation of one or more con-stituents from the solid solution. The similarity between the solid solubility curves of such alloys (Fig. 1) and those for iron-nitrogen (Fig. 2) and iron-carbon alloys (Fig. 3) below the Al transformation point suggested at once that magnetic aging of iron might be caused by a similar process; namely, by the slow precipitation of carbon and nitrogen in the form of Fe4N and Fe3C at ordinary temperatures because of a cooling rate that had been too rapid to permit complete precipitation according to equilibrium conditions. This suggestion has since been amply confirmed, particularly by the comprehensive work of Köster1 on the effect of nitrogen and carbon. Typical curves are shown in Fig. 4 for the relationship between aging temperature and coercive force. Previous to the establishment of the precipitation-hardening theory it was thought that the effect of nonmetallic elements like C, N, 0, etc., on the magnetic properties of iron was greatest when these elements were retained in solid solution, atomically dispersed throughout the interstitial spaces of the iron lattice2.

Jan 1, 1935

LARGEST known fluorspar deposits in the world are mined in southern Illinois (Hardin County), and northwestern Kentucky (Crittenden County). Colorado, New Mexico, Montana, and Utah are the principal western sources in the U. S. Rosiclare Fluorspar District Hardin County, Illinois The Rosiclare area is located in the southern part of Hardin County on the Ohio River where the Illinois Central Rd. branch line terminates and provides transportation. Fluorspar has been mined commercially in this area since 1870. Aluminum Co. of America and Rosiclare Lead & Fluorspar Co. are the two major producers in this area. Ozark-Mahoning Co. operates a concentrating plant in Rosiclare but the bulk of its ore is mined near the town of Cave-in-Rock.

Jan 1, 1958

By Don B. Shupe, John K. Berry

The handling and disposal of mine water is a much larger problem than is apparent at first glance. Many more tons of water are removed from underground coal mines in the United States each year than tons of coal. In the old anthracite region of Pennsylvania the average was around 32.7 t (36 st) of water for each ton of coal produced, while bituminous mines average about 4.5 or 5.4 t (5 or 6 st). Water encountered in the mines may come from several different sources. In mines with light cover and without a firm solid roof, rain may seep directly into the workings. This is also true of deeper mines where pillar falls have broken the roof to the surface. The top under creek beds is generally faulty and broken and water comes through the roof at this point. Deeper mines are frequently overlain by water-bearing strata and pillar breaks and faulty top can admit water, while places running to the dip often accumulate water which comes up through the bottom. In all cases, except where passing under a year-round stream, the amount of water made is usually pretty closely connected with the weather-more water during the rainy season, less in the dry, although the deeper a nine is, the longer it is before changes in rainfall are felt. Another source of water, not connected with seasonal changes, is old water, accumulated over a period of time in abandoned workings of the mine, or from flooded adjacent mines. Here the water filters through the coal, the parting, or comes up through cracks in the bottom. Similarly, core holes, drilled to prospect the property, can be a source of unexpected water and modern safety requirements for dust-allaying water at the working faces can turn a pleasant working area into a soggy mess over the weekend if the system is not properly maintained and operated. Why water must be disposed of is obvious. If allowed to accumulate, sooner or later the mine will fill up, or at least it will become "roofed" in low places, blocking ventilation and traffic. It must be controlled long before it reaches this stage. Water standing in the working faces is

Jan 1, 1981

By A. L. Pranatis, G. M. Pound

Changes in length of copper foils of varying thickness and grain size were measured under such conditions of low stress and high temperature that it is believed that creep was predominately the result of interboundary diffusion of the type recently discussed by Conyers Herring. The surface tension of copper was calculated and results confirmed previous work within the limits of experimental error. Under the assumption of viscous flow, viscosities were calculated as a function of temperature and grain size. Predictions of the Nabarro Herring theory of surface grain boundary flow were borne out fully and the Herring theory of diffusional viscosity is strongly supported. ONLY a relatively few techniques for obtaining the surface tension of solids are presently available. Of these, the simplest and most straight forward is the direct measurement of surface tension by the application of a balancing counterforce. Thin wires or foils are lightly loaded and strain rates (either positive due to the downward force of the applied load or negative if the contracting tendency of surface tension is sufficiently greater than the applied stress) are observed. By plotting strain rates against stress, the load which exactly balances the upward pull is found and a simple calculation yields a value for the surface tension. The technique is of comparative antiquity, and solid surface tension values were reported by Chapman and Porter,' Schottky; and Berggren" in the early part of the century. Later, the filament technique became fairly well established as a method for determining the surface tension of viscous liquids, and Tammann and coworkers,'. " Sawai and co-worker and Mackh howed good agreement between the values of surface tension for glasses and tars obtained by the filament technique and by more conventional methods. With the increased confidence in the technique gained in these experiments, the method was applied to solid metals and the first reliable values of surface tension of solid metals were reported by Sawai and coworkers10' " and by Tammann and Boehme." More recently, Udin and coworkersu-'" have reported the results of experiments with gold, silver, and copper wires. Similar experiments with gold wires were carried out by Alexander, Dawson, and Kling.'" The excellent review articles of Fisher and Dunn" and of Udinl@ should be referred to for detailed criticism of the foregoing work and for discussion of underlying theory. In all the foregoing calculations, it is assumed implicitly that the material contracts or extends uni- formly along the length of the specimen and also that it flows in a viscous fashion, i.e., that strain rates are proportional to stress. For an amorphous material, such as glass, tar, or pitch, the assumptions are quite valid and good agreement is obtained with values of surface tension measured by other techniques. The values reported for metals, however, are occasionally regarded with misgiving, since it can be argued that, because of their crystalline nature, true solids can not deform in a viscous fashion. If this is true, then the results reported for solid metals over a long period of years are of only doubtful value. Thus it is clearly necessary that a mechanism be established that would explain both the viscous flow and the uniform deformation that has been assumed. Such a mechanism has been proposed by Herring."' Briefly, he suggests that, under the conditions of the experiment, deformation takes place by means of a flow of vacancies between grain boundaries and surfaces. This is a direct but independent extension of the theory proposed by Nabarro" in an attempt to explain the microcreep observed by Chalmer~.In a condensed form the Herring viscosity equation is TRL there 7 is the viscosity, T the absolute temperature, R and L grain dimensions, and D the self-diffusion coefficient. In its complete form, all constants are calculable and it includes such factors as grain shape, specimen shape, and degree of grain boundary flow. When applied to existing data, good agreement was obtained between predicted and observed flow rates. The theory received provisional confirmation from the work of Buttner, Funk, and Udin" who observed viscosities in 5 mil Au wire much higher than those in the 1 mil wire used by Alexander, Dawson, and Kling.'" More significant were the completely negligible strain rates found by Greenough" in silver single crystals. Opposed to these observations were those of Udin, Shaler, and Wulff'" who found indications of viscosity decreasing as grain size increased. Thus, complete confirmation of the theory was lacking in that the data to which it could be applied contained only a limited number of grain sizes. Hence, it was proposed that a series of experiments be carried out with thin foils of varying grain size up to and including single crystals, where, according to the Herring theory, deformation would occur only at almost infinitely slow rates.

Jan 1, 1956

By William Wraith

1. INTRODUCTION. AT the Washoe smelter,. Anaconda, Mont., the blister-copper from the converters is transferred, by means of a crane, to a refining-furnace,, in which it is brought to proper pitch by means of air and poles. From this furnace the refined copper, containing gold and silver, is poured into cast-iron molds placed on a platform-conveyor, giving an anode 36.75 in. long, 28 in. wide, and 21 in. thick. By reason of a disagreement between the smelter and the refinery, in reference to the silver-content of the anodes, it became necessary to investigate the methods of sampling used. II. SMELTER METHOD OF SAMPLING. At the smelter the sampling is done by " spotting " into water a small portion of the molten stream of copper as it flows from the furnace, by batting" the stream with a wooden paddle. The first sample is taken 30, min. after the pouring is started, three. other samples being taken at 1-hr. intervals, each sample weighing from 4 to 6 oz. The samples are dried, examined for particle's of burnt wood, screened on a 10-mesh screen of No. 8 wire to remove the fines, the oversize then screened on a 4-mesh screen of No. 20 wire to remove the coarse, the undersize of this screen being taken as the sample. Teh four portions thus obtained are thoroughly mixed and spli in half by passing over a 16-slot splitting-device, slots being 0.5 in. wide. One-half of the sample is sent to the laboratory for analysis and one-half kept as a duplicate. III. REFINERY METHOD OF SAMPLING. The method used at the refinery and also used in this investigation is the one developed by Dr. Edward Seller, of

Mar 1, 1910

By H. Doi, Y. Fujiwara, K. Miyake

In order to throw light on the mechanism of plastic deformation of WC-Co alloys, compressive tests of WC-(7 to 43) vol pct Co alloys have been carried out at room temperature, and stress-micro strain relation has been investigated in detail. The analysis of the factors affecting the yield stresses reveals that the yield stresses can be predicted by modified Oro-wan's theory if one properly estimates the planar in-terfiarticle spacings. Conzpressive straining of some of the alloys by 0.066 to 0.17pct increases the decrements by a factor of as much as 3.4 to 14, whereas the corresponding increase in the electrical resistivities is less than 10 pct. The analysis of the decrement data in terms of -Gramto and Lücke theory shows that the marked increase is attributed to increased dislocation darnping itt the binder (cobalt) phase. By cornbilling the decrement data and the conzjwession duta, one obtains the relation between flow stress in shear (?t) and increase in dislocation density (p): At = const . v6 . This is interHeted to mean that the mechanism of strain hardening of CirC-Co alloys is essentially sarne as the one for dispersion strengthened alloys. The possible effect of bridge formations between the carbide particles has also been examined. OWING to the combination of hardness, strength, and other physical and chemical properties, WC-Co alloys have opened the way for unique fields of applications, the recent ones being, for instance, anvils for super-high-pressure generation apparatuses. In such applications, the alloys are frequently subjected to very high compressive stresses: these stresses may cause the alloys to deform plastically and eventually to fail. However, much remains obscure regarding the nature of the plasticity of the alloys. Evidently, the alloys owe their high strength to the hard carbide particles which frequently occupy as much as 80 to 90 pct in volume fraction, whereas the ductility required for practical applications is provided by the small amount of the binder phase between the carbide particles. When the volume fraction of the carbide phase is not very large, deformation behavior of the alloys may be described by some of the current dispersion strengthening theories. However, greatly increasing the carbide phase is thought to lead to some carbide skeleton structure or bridge formations owing to the increased chances for direct contacts between the carbide particles;1,2 this may appreciably affect the plasticity of the alloys. Regarding the effect of formation of the carbide skeleton structure, it is interesting to note the work by Ivensen et al.3 on compression tests of the alloys containing somewhat large carbide particles; they observe extensive generation of slip bands in the carbide particles after application of some preliminary compressive stresses. They interpret the results in terms of plastic deformatiot: of the carbide particles which are supposed to have formed a skeleton structure; the binder phase plays only a passive role, at least in the early stages of the deformation. That carbide crystals exhibit microplasticity at room temperature is apparent from the work of Takahashi and Freise4 and French and Thomas5 on indentation of WC single crystals. On the other hand, Dawihl and coworkers6-10 maintain that even when volume fraction of the carbide phase is very large (for instance, more than 90 pet), a very thin binder layer generally exists between the carbide particles. They interpret the results of the extensive mechanical tests in terms of the plasticity of such a layer. Gurland and Bardzil11 point out that decrease in ductility of the alloys with increase in the carbide phase is caused by the effect of plastic constraint exerted by the dispersed carbide particles. Drucker12 further develops this concept from a continuum-mechanics approach on an assumption that a continuous thin binder layer separates the carbide particles. A common feature of the studies reported so far on the plasticity of the alloys is that the information deduced is invariably qualitative in nature. Thus, very few systematic experiments for obtaining reliable and sufficiently detailed stress-strain curves of the alloys varying widely in the microstructural features have been carried out. In particular, it may be of special interest to investigate in detail the early stages of the plastic deformation of the alloys in order to shed light on the strengthening mechanism. However, such work appears to be extremely rare. Doi et al.13 recently reported a first brief account of the results of some quantitative analysis of the plasticity of the alloys in terms of dislocation theory. Their experiment was rather limited in the composition range covered (volume fraction occupied by the carbide phase: 79 to 83 pct), and thus they could not necessarily elucidate the controlling mechanism of plastic deformation of the alloys of a more general composition range. Consequently, in the present investigation, deformation behavior and some other physical properties of the alloys were investigated and discussed in more detail over a much wider composition range. SPECIMEN PREPARATION WC-Co alloys used in this experiment were prepared in cylindrical or rectangular form by sintering in vacuo compressed mixtures of tungsten carbide and cobalt

Jan 1, 1970

[Abstmct of remarks by R. II. Sweetser arid suhscqueut discussion at the New York Meeting, February, 1926. The Transactions mill ultimately contain a report of work resulting from these discussions. Need for a standard of ualuration.—There should be an accepted method for evaluating the different kinds of bituminous coals based on their carbon just as that for iron ores is based on iron. Variation in the classes of coals and their desirability fol the different industrial uses is analagous to the case of iron ores. The iron people have developed a standard. In the past coals have not been intelligently distributed because the public has not been informed as to its uses. Many operators have known nothing about the final disposal of the coal shipped from their mines. Sales agents and retailers have had no means of evaluating coals except to make the price as high as the market will stand. Producers and distributors need to know how much more valuable the coals would be if prepared so as to contain less objectionable material. Mr. Swectser cnlletl on the Goal and Coke Committee of the Institnte to organize a study through producers and users to develop a method scientifically and comnereially sound E. A holbrook said that the information exists but the public is unwilling to investigate. He praised Ashley's1 nomenclature of the different kind of coal which has been accepted by the Coal Mining Institute of America and recommended to the American Enginecring Standards Commitee. G. S. Rice pointed out the wider variety and distribution of consumption of coal compared to Iron ore. C'. M. Young approved Mr. Sweetser's remarks and hoped lor a research institution, probably endowed, to study utilization of coal after it comes from the ground. Mr. Sweetser cited incidents to prove his former statements. He said that a reduction of 1 per cent. ash in the coal would cut down the cost of pig iron at a blast furnace 30 c. a ton, that the coal men should tell what the iron men would have to pay to get better coal. H. J. Prryn endorsed the need of blast-furnace operators to know the kind of coal from which their- coke is made and the latler's ash content, as this affects coke consumption. A. C. Fieldncr explained that the difficulty of evaluating coal on the basis of chermical analyses for calorimetric tests is: (1) representativr

Jan 1, 1927

By T. D. Yensen, N. A. Ziegler

AGING is a term that connotes a slow change in properties under ordinary operating conditions. It can be accelerated by increasing the temperature and by mechanical straining. The magnetic properties of iron and some of its alloys have for many years been known to be subject to such a change. But the cause of the change was not recognized until a few years ago after mechanical age-hardening in nonferrous alloys of the "duralumin" type had been definitely shown, by means of solid solubility curves, changes in electrical resistance and microanalysis, to be caused by slow precipitation of one or more constituents from the solid solution. The similarity between the solid solubility curves of such alloys (Fig. 1) and those for iron-nitrogen (Fig. 2) and iron-carbon alloys (Fig. 3) below the Al transformation point suggested at once that magnetic aging of iron might be caused by a similar process; namely, by the slow precipitation of carbon and nitrogen in the form of Fe4N and Fe3C at ordinary temperatures because of a cooling rate that had been too rapid to permit complete precipitation according to equilibrium conditions. This suggestion has since been amply confirmed, particularly by the comprehensive work of Köster1 on the effect of nitrogen and carbon. Typical curves are shown in Fig. 4 for the relationship between aging temperature and coercive force. Previous to the establishment of the precipitation-hardening theory it was thought that the effect of nonmetallic elements like C, N, 0, etc., on the magnetic properties of iron was greatest when these elements were retained in solid solution, atomically dispersed throughout the interstitial spaces of the iron lattice2.

Jan 1, 1935

Coal Division Industrial Minerals Division Minerals Beneficiation Division Mining, Geology and Geophysics Division Elmer A Jones, President President-elect Will Mitchell, Jr, Past President J B Morrow, Eastern Regional Vice-President G Donald Emigh, Central Regional Vice-President J D Forrester, Western Regional Vice-President R B Ladoo, Treasurer John Cameron Fox, Secretary AIME 29 West 39 St, New York 18, N Y

Jan 1, 1957

By Frank W. Bowdish, T. M. Plouf

The purpose of this writing is to make available additional data, not previously published, on the zeta potential at various pH values of chrysocolla from the Inspiration mine, Arizona. Much research has been performed on chrysocolla, its physical properties, and its flotation, the results of which have not yielded a commercially acceptable flotation process for its recovery. The present data were collected and are presented to further advance chrysocolla research. Experimental For this investigation a carefully prepared sample of chrysocolla was used. This sample was obtained by crushing specimens from the Inspiration mine and picking out by hand the solid blue particles at -3+8 mesh, by grinding these to 10 mesh and repicking the +28 mesh sizes, by cleaning this product using magnetic separation, and by grinding and screening the material into fractions for final magnetic treatment on a Frantz Isodynamic Separator. All testing was done on the -100+150 mesh fraction. A chemical analysis was made on a portion of this fraction which was washed in dis-

Jan 1, 1974

By J. W. Pamplin

SOME 40 miles east of Tampa is the center of the Florida pebble phosphate deposits. These are of Pliocene age and consist of several members of the Bone Valley formation.' Physically the phosphate-bearing formation, locally called the “matrix," varies in thickness from nothing to about 25 ft., usually averages 10 ft., and consists mainly of clay, quartz and phosphate pebble, the latter particles varying in size from colloidal to one inch diameter. The pebbles range in color from dark gray, through white, to cream, and in hardness from that which must be broken with a hammer to that which can be scratched with the fingernail. They assay from 66 to 80 per cent bone phosphate of lime (called "B.P.L." in the trade) or tricalcium phosphate (Ca3P2O8) and are secondary apatites. They form from 15 to 50 per cent by weight of the matrix. Over the matrix lies a varying thickness (5 to 40 ft.) of overburden composed of quartz and clay. Briefly, mining consists of two operations2 in open pits about 200 ft. wide by ½ mile or more in length. In the first step overburden is removed by large electric draglines at the rate of about 700 cu. yd. per hour. This is followed closely by hydraulic mining of the matrix at the rate of about 300 cu. yd. per hour. This matrix yardage is moved from an improvised sump in the floor of the pit to an ore-dressing plant, some- times a mile distant, by one, two or three "pit-cars" (pumping units) working on a 12-in. pipe line called the "rock line" to distinguish it from the high-pressure water line feeding the hydraulic giants, which is known as the “hydraulic line." This 700 yd. of overburden and 300 yd. of matrix-1000 yd. in all- amounts to about 1500 tons of material moved each hour. The over- burden is dumped into the mined-out pit alongside the pit being mined. The matrix moves to the ore-dressing plant at the rate of about 7 ½ long tons in 4000 gal. of water per minute-a ratio of approximately one to two by weight, or one to six by volume. This constitutes the "mill heads," but in the pebble district it is called the "matrix."

Jan 1, 1938

By D. A. Lyon

Discussion of the paper of DORSEY A. LYON and ROBERT M. KEENEY, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. 1707 to 1730. LAWRENCE ADDICKS, Douglas, Ariz.-I think papers of this character, while general in, nature, are of particular value and interest, because when we figure on competing with the East in electrometallurgical industries, on account of the cheap power on the Pacific Coast, we have to take two or three things into account. In the first place, power very rarely amounts to more than 20 per cent. of the total cost of an operation, even .though it be electrometallurgical, and I think it is the common opinion among those who are not familiar with those particular industries, that it amounts to more than 50 or 60 per cent. Take copper refining; we may say that it is 15 per cent. of the total cost. In the second place, around New York City, with 100 per cent. load factor and a reasonably large load, say 10,000 kw., we can generate from a certain class of coal 1 kw.-hr. for about 0.3c. I might say, however, that 0.3c. does not include overhead charges, interest on the investment, etc. The third factor we have to consider out here is that any product to be salable, must command a retail market. It would be useless to produce wire bars here on the Pacific Coast because there is no place to roll them. If we were going to establish a copper refinery, that part of its output which goes into wire bars would have to be taken care of by building a rolling mill alongside of it to turn it into wire and finally make a product that is salable. I do not think, however, that Mr. Lyon need have excluded copper refining from his industries. There are perhaps 50,000,000 lb. of copper a month refined in this country on a custom basis. I think the smelting companies would be very glad to build refineries here if conditions warranted it. The recent extensions of the Great Falls refinery and of the Tacoma refinery in the last few months give evidence of that.

Jan 12, 1915

By MCA Woolsey

(Butte. Meeting, August, 1913.). IN metallurgical circles it is known widely, but somewhat vaguely, that the ease of: reduction of metallic oxides depends largely on the way they have been prepared. It is likewise known that different forms of carbon have different and greatly varying reducing powers. It is the purpose of this paper to show somewhat more definitely and scientifically these facts. Some years ago the writer published an account of pyrometric determinations of the reduction- temperature of zinc oxides variously prepared and of several kinds.1 In said paper it was shown that the temperature it which zinc oxide evolves zinc according to the equation Zn0. +' C = Zn + CO depends upon the ;nature of:., the.' two reacting bodies. The determinations bad a range of accuracy of from 2° to. 6° C.,whereas differences were found to. amount to an extreme. of 90° C. :.86 the differences are real ones and must have, definite cause. The equation of boiling water, (H20)4 = 4 (H2O) has a fixed temperature for equilibrium of 100° C. at 760 mm. pressure. , In general, all equations. reacting e in .the liquid or the gaseous phase have-well-defined constant physical conditions which govern the equilibrium point and reaction velocities. In a reaction where we have one or more solid phases, the temperature conditions requisite for the unbalancing of the stable system are found to vary. These variations are due to the fact that in a solid there is a very complex molecule and it is not, a question solely of the tearing away of two interlocked atoms, but also of the destruction of a complex molecule containing hundreds, or possibly thousands, of smaller molecules.

Jan 7, 1913

By Jerome Alexander

It is an outstanding fact of Nature that many of the practical properties of substances are dependent, not on their ultimate chemical composition, but on the kind and degree of aggregation of their constituent particles. Thus, a granite boulder is unmoved by wind or water, but if reduced to a fine dust it will be blown about by the wind and washed away by the rain. Carbon in one crystalline state of aggregation (diamond) is the hardest known substance, whereas in another crystalline state (graphite) it is so soft that it is used as a lubricant. Laying too much stress on the mere chemical analysis of substances is apt to obscure the fact that the nature of the aggregation of their particles is always a factor of importance, and sometimes the most important factor. Colloid chemistry deals with matter in a very fine state of subdivision; its sphere begins with particles just a little smaller than a wave length of light and extends down until they blend into molecular dimensions. With particles of this size, such phenomena as surface tension and adsorption, which depend on the development of free surface, become enormously magnified. Thus a cube of 1 cm. edge has a surface of only 6 sq. cm.; but if it is reduced to colloidal dimensions by being cut up into cubes each having an edge of 0.01 µ (0.00003 mm.), it will yield one million, million, million (1,000,000,000,000,000,O~) such cubes, having a combined area of 600 sq. m., or 21,274 sq. ft. The tiny force with which a drop of rain clings to the window pane becomes a factor to be reckoned with, if the surface involved is increased millions of times. From the colloid-chemical viewpoint, metals and alloys may be regarded as jellies or sponge-like structures,. the viscosity or stiffness of which at ordinary temperatures is exceedingly great; and like all jellies their properties are dependent on the composition and degree of dispersion of their constituent phases. These, in turn, depend on chemical composition, mutual solubility, speed of chilling, subsequent mechanical and heat treatment, etc. In fact, in preparing metals and alloys for practical use, we remove undesirable constituents (as in the conversion of pig iron into steel), add desirable constituents (as in

Jan 1, 1919

By C. R. Barrett, N. N. Singh Deo

The high-temperature steady-state creep behavior of a series of dilute copper-silicon alloys was studied to determine the effect of stacking fault energy on the creep-rate. The steady-state creep rate is, when taken at equivalent diffusivities decreases with decreasing stacking fault energy. The stress and temperature dependencies of is suggest that creep is a difusion controlled dislocation climb process. Electron microscopy studies of the creep substructure revealed: 1) the subgrain size is not a function of the stacking fault energy in these alloys, 2) the dislocation density not attributed to the subgrain walls seems to be higher during primary creep and decreases to a lower steady value during steady-state creep, and 3) the dislocation density during steady-state creep decreases with decreasing stacking fault energy. In the past few years numerous investigators have studied the influence of stacking fault energy on high-temperature creep strength. Most of these investigators have confined their attentions to studying the relationship between steady-state creep rate, is, and stacking fault energy, ?, when samples are tested under conditions of comparable stress and temperature. For the case of fcc metals, it was initially shown by Barrett and Sherbyl and since confirmed by many others2"4 that is decreases with decreasing ?, often following an empirical relation of the form i ?m where m is a constant about equal to 3. The application of theory to explain this observation has not been entirely successful. One of the main difficulties has been the almost complete lack of structural information (dislocation density, subgrain size, and so forth) for samples with different stacking fault energies, tested under high-temperature creep conditions. weertman5 has attempted to explain the stacking fault energy dependence of is on the basis of a dislocation climb mechanism. Assuming that both the rate of dislocation core diffusion and the ease of athermal jog formation decreases as ? decreases Weertman has argued that the rate of dislocation climb and hence the creep rate should also decrease as ? decreases. One questionable aspect of Weertman's analysis is the assumption that core diffusion down extended dislocations is slower than core diffusion down unextended dislocations. The only experimental work done in this area, by Birnbaum et al.6 on nickel and Ni-60 Co, has shown the core diffusivity to increase with decreasing ?. Theories of steady-state creep based on the diffusive motion of jogged screw dislocations often seem unable to predict even the qualitative nature of the es- relationship. Assuming that Weertman is correct in his assumption that the dislocation jog density decreases with decreasing ? then the jogged screw theories predict an increasing dislocation velocity with lower ?. It is usually assumed that the increase in dislocation velocity implies a corresponding increase in creep rate. However, two other factors must be considered before such a statement can be made. That is, we must know how both the mobile dislocation density and the effective stress (the difference between applied stress and internal stress) vary with ?. Significant changes in either one of these factors could outweigh any change in dislocation velocity accompanying a change in ?. And with the slower rates of recovery expected in low stacking fault energy materials it seems likely to expect both mobile dislocation density and effective stress to be dependent on ?. Sherby and Burke7 have suggested that stacking fault energy influences the creep rate in an indirect way. These authors cite evidence that the steady-state subgrain size generated during high-temperature creep is a function of ? decreasing with decreasing ?. Assuming the creep rate to be proportional to the area swept out by each expanding dislocation loop and that subgrain boundaries are good barriers to dislocations, then the creep rate should be proportional to subgrain area, hence increasing as ? increases. A critical evaluation of any of the above theories requires more quantitative information concerning the dislocation substructure generated during high-temperature creep. Accordingly this investigation was undertaken with an aim of studying the influence of stacking fault energy on tbe steady-state creep characteristics of a series of dilute copper-silicon alloys. Special emphasis was placed on studying the strain dependence of both the dislocation configuration and density. MATERIALS AND PROCEDURE Dilute copper-silicon alloys of the compositions shown in Table I were tested in tension at constant stress. The relative stacking fault energy of these alloys has been determined and is shown in Table 11. An Andrade-Chalmers lever arm was used to maintain constant stress and testing was carried out in a water

Jan 1, 1970

By E. L. Mann

Asbestos is the generic name given to a group of fibrous mineral silicates found in nature. They are all incombustible and can be separated by mechanical means into fibers of various lengths and cross sections, but each differs in chemical composition from the others. The commercial grades of asbestos consist of a spectrum of lengths and sizes and are not definitive as are most organic fibers. It is generally recognized that there are two main groups of asbestos. The first only contains the fibrous serpentine called chrysotile and comprises about 94% of the world production of asbestos. The second group contains five minerals in the amphibole series-crocidolite, amosite, anthophyllite, tremolite, and actinolite. The latter two have no commercial importance. Properties Physical The structures of asbestos fibers have been studied intensively over a number of years. X-ray diffraction patterns have been used as a means of identification and classification. Low angle X-ray scattering techniques have shown that chrysotile fibers are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 18Å to 300 Å units, while the amphibole fibers are many times larger in cross section, have considerably smaller surface areas, and the fibers are less symmetrical than those of chrysotile. Electron micrographs of the more common types of asbestos are shown in Figs. 1-4. Fig. 1 illustrates the softness and flexibility of chrysotile which make it suitable for textile-type products. For a number of years there was considerable controversy over the exact nature of chrysotile fiber, but the photographic evidence in Figs. 5-7 clearly show that it is tubular in structure. The curvature is the result of the mismatch in the dimensions of the silica [Si2O5] and brucite [Mg(OH)2] layers which are on the inside and outside, respectively, of a double sheet. This curvature had been predicted by Pauling (1930) years ago based on the molecular dimensions of the two component structures. In contrast to this, the structure of the amphiboles consists of two ribbon chains based on Si4O11 units separated by a band of seven cations with two hydroxyl groups attached to

Jan 1, 1983

Discussion of the paper of Reno H. Sales, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 80, August, 1913, pp. 1524 to 1626. L. C. GRATON, Cambridge, Mass.:-It has been my privilege to read with some care Mr. Sales's paper, and I feel it a sense of duty and a pleasure to discuss it briefly. After two months spent underground in the Butte mines by my associates-Messrs. Augustus Locke, A. M. Bateman, and E. H. Perry-and myself, it seems only fair to record our appreciation of the almost baffling structural complexity of the Butte veins, of the remarkable accuracy with which their mechanical details have been worked out, and of the unusually effective and intelligent use of geologic conceptions in interpreting their subtler characters and significance. During this period, under the courteous and helpful guidance of either Mr. Sales, the members of his staff, or the geologists of other companies, we have been afforded opportunity to test many of the conclusions embodied in the present paper, and it is but just to state that as our observations have accumulated sufficiently the great majority of these conclusions have received unquestioned confirmation in our minds. The pleasure consists in realization that the science of mining geology, to which so many of us have devoted ourselves, actually embraces the possibilities that this paper exhibits. The science of geology has been favored by many brilliant contributions of general nature, and by a smaller number of studies remarkable because of their detail and precision. I know, however, of no other piece of work like this, which, including Mr. Winchell's administration, virtually represents the combined results of over 15 years of work by a staff of trained geologists in a district which measures not much more from end to end than it now does from top to bottom. That this concentration of effort and observation has been required, and that it has been repaid by the results attained, are plentifully evident in Mr. Sales's paper. If one were inclined to doubt this after perusal of the text, surely he would be convinced by the maps and sections, several of which, I venture to say, are unapproached in detail and accuracy by anything attempted before.

Jan 11, 1913

By Elmars Ence, Harold Margolin

A. J. Goldak and J. Gordon Parr (University of Alberta) —While we appreciate the difficulties involved in any investigation of this system, and we wish to congratulate the authors on their comprehensive efforts, there are several aspects of their paper that are not clear to us. 1) If the 6 phase is, in fact, isomorphous with Ti3Sn, it should not be designated Ti,Al. An 4B structure cannot be isomorphous with an ordered structure of the DO type. Anderko et al.' suggested that the structure be called Ti3A1, and we believe this to be a more reasonable designation. The confusion is compounded when the authors designate the phase Ti3Al—yet the composition limits of this phase (according to their diagram) are approximately Ti,A1 and Ti,Al. Further, while Pietro-kowsky is said to have pointed out that the structure of the 6 phase is isomorphous with Ti3Sn, we understand that this was only a suggestion that was not confirmed. Margolin and Ence do not appear to have presented any evidence to support the suggested isomorphism. 2) In referring to the precipitation observed microscopically during the initial breakdown of high A1 a during quenching, the authors state that "such precipitation is not likely to be detected by Debye-Scherrer techniques". We suspect that if the precipitate was visible by optical microscopy, it must have at least one dimension of the order of 1 or greater, and would therefore be readily detected by diffraction techniques. 3) The authors state: "The basis for this suggestion (that 6 forms peritectically P + L—6) is the observation that the ,'3 + 6 and 6 phase fields were

Jan 1, 1962

By J. W. Pamplin

SOME 40 miles east of Tampa is the center of the Florida pebble phosphate deposits. These are of Pliocene age and consist of several members of the Bone Valley formation.1 Physically the phosphate-bearing formation, locally called the "matrix," varies in thickness from nothing to about 25 ft., usually averages 10 ft., and consists mainly of clay, quartz and phosphate pebble, the latter particles varying in size from colloidal to one inch diameter. The pebbles range in color from dark gray, through white, to cream, and in hardness from that which must be broken with a hammer to that which can be scratched with the fingernail. They assay from 66 to 80 per cent bone phosphate of lime (called "B.P.L." in the trade) or tricalcium phosphate (Ca3P20s) and are secondary apatites. They form from 15 to 50 per cent by weight of the matrix, Over the matrix lies a varying thickness (5 to 40 ft.) of overburden composed of quartz and clay. Briefly, mining consists of two operations2 in open pits about 200 ft. wide by ½ mile or more in length. In the first step overburden is removed by large electric draglines at the rate of about 700 cu. yd. per hour. This is followed closely by hydraulic mining of the matrix at the rate of about 300 cu. yd. per hour. This matrix yardage is moved from an improvised sump in the floor of the pit to an ore-dressing plant, some-times a mile distant, by one, two or three "pit-cars" (pumping units) working on a 12-in. pipe line called the "rock line" to distinguish it from the high-pressure water line feeding the hydraulic giants, which is known as the "hydraulic line." This 700 yd. of overburden and 300 yd. of matrix-1000 yd. in all-amounts to about 1500 tons of material moved each hour. The over-burden is dumped into the mined-out pit alongside the pit being mined. The matrix moves to the ore-dressing plant at the rate of about 7 ½ long tons in 4000 gal. of water per minute-a ratio of approximately one to two by weight, or one to six by volume. This constitutes the "mill heads," but in the pebble district it is called the "matrix."

Jan 1, 1938