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By John Johnston

When I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe's book, "The Metallography of Steel and Cast Iron," published in I9I6—that is, about 25 years ago—in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father— Dr. Samuel Gridley Howe, his mother— Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe's writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature, is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-clrbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable. tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass ... by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half-initiated from misusing it and the uninitiated from being misled by these misuses," he writes—and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration: It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. it tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works of the watch was the best butter. If the reader learns no more than to beware of attempts to dccipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942

By L. R. Duncan, O. M. Wicken

Magnesium, the eighth most abundant element in the earth's crust, is found widely distributed in a variety of minerals. Among the more commercially important ones are magnesite (MgCO3), brucite (Mg[OH]2), dolomite (CaMg[C03]2), and the salts magnesium sulfate and chloride often found in natural brines. Among other commercially important magnesium-containing minerals are olivine ([MgFe]2Si04), talc (H2Mg3[Si03]4), and serpentine (H4Mg3Si2O9). These are valuable because of desirable characteristics given them by the magnesium content and its placement in the particular crystal structure. These minerals are the raw materials for a host of products including magnesium metal and several grades of magnesia or magnesia-containing materials for refractories, fluxes, fillers, insulation, cements, decolorants, fertilizers, and chemicals. Considering only those minerals valued for their magnesia or magnesium content, over 85% of the material tonnages are processed to be used as refractories. Dolomite, which is used in enormous tonnages for its physical properties in construction, has an important use as a refractory raw material in its own right and, after calcination, as a precipitant for magnesium hydroxide, which is an intermediate for the production of magnesia or magnesium metal. Magnesia from the reaction of calcined dolomite (or limestone) with seawater or magnesium-containing brines has supplanted much of the production of magnesia from mined magnesite, particularly in the United States. The best known of the minerals directly and widely exploited for magnesia content is magnesite, one of the calcite group of rhombohedral carbonates which includes calcite (CaC03), siderite (FeCO3), and rhodochrosite (MnCO3) among others. The members of this group enter into a wide range of substitutional solid solutions when the positive ions have similar radii. The radii of magnesium and iron ions are within 6% of each other; hence, magnesite and siderite form a complete series of which breunnerite (ferroan magnesite) is a well-known end member. However, the radius of calcium ion is 36% larger than that of magnesium ion, and only limited substitution exists at each end of the MgCO3-CaCO3 series. Dolomite is not a member of the calcite group, but results when calcium and magnesium ions alternate in equal number in an ordered structure among carbonate ions. The result of these relationships is that calcite and dolomite, often found intermixed with magnesite, occur commonly as identifiable crystal entities which can often be separated to a varying degree from the magnesite by various beneficiation techniques. Magnesite, when pure, contains 47.8% MgO and 52.2% CO.. The pure mineral is sometimes, but rarely, found as transparent crystals resembling calcite, but, preponderantly, magnesite contains variable amounts of the carbonates, oxides, and silicates of iron, calcium, manganese, and aluminum. Magnesite may be either crystalline or amorphous (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black with shades of yellow, blue, red, or gray. The color is not a fundamentally significant indicator of purity, but in a given deposit, an experienced person can often roughly grade magnesite by assessing color and crystallinity. The crystalline form of magnesite occurs in

Jan 1, 1983

By John Johnston

WHEN I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe's book, "The Metallography of Steel and Cast Iron," published in 1916-that is, about 25 years ago-in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father Dr. Samuel Gridley Howe, his mother Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe's writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature, is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-carbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand' truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable, tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass ... by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half¬initiated from misusing it and the uninitiated from being misled by these misuses," he writes-and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration: It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. It tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works of the watch was the best butter. If the reader learns no more than to beware of attempts to decipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942

By J. S. Osoba, J. W. Graham, P. H. Monaghan

Of the many factors which affect the productivity of hydraudically fractured wells, the wettability of the propping sand has received little attention in the pas/. This paper shows that the wettability of the propping sand is an important factor which shorcltl not he overlooked. An analysis of relative permeability data shows that fractures packed with water-wet sand should be more permeable to oil than are fracturer packed with oil-wet sand. Laboratory results verify this conclusion. Cnlculations show that higher permeability to oil in the fracture should provide higher well productivity. A method is presented which ensures that the propping sand in an induced fracture is water-we1 even though oil is used as the fracturing fluid. The rnethod has been used in more than 150 field jobs: the field resrrlts are discussed briefly. The fluidized nature of water-wet sand in oil has giver1 unexpected benefits. This characteristic of water-wet sand and how it has been used advantageously in field operations are discussed. INTRODUCTION Hydraulic fracturing of subsurface strata to increase the productivity of oil and gas wells has been practiced for about 10 years. Today, fracturing is used more often than any other method of well stimulation. Basically, the process consists of breaking down (fracturing) a subsurface formation with pressure applied by means of a carrier fluid, usually oil or water, and propping the induced fractures apart by means of an agent, usually sand. suspended in the carrier fluid. Currently about 68 per cent of all fracturing is done with a simple mixture of refined oil or lease crude oil and sand'. The research of other investigators has suggested that dry sand is rendered oil-wet when it is contracted with certain types of crude or refined oils.' Hence, it may be expected that some fracturing operations employing an oil as the carrier for sand leave fractures packed with oil-wet sand. Conversely, those operations which employ water as the carrier for the sand probably leave the fractures packed with water-wet sand. Since the permeability of a sand-packed fracture to a mixture of oil and water is dependent upon the wettability of the fracturing (frac) sand, research was undertaken to determine to what extent the wettability condition (water-wet or oil-wet) controls fracture permeability which, in turn, affects well productivity. Additional research was directed toward the development of a method for obtaining the desired fracture wettability. In this report both theoretical and experimental evidence is presented to show the desirability of employing water-wet sand in fracturing operations. A method to obtain water-wet sand is discussed, and field results are reviewed briefly. DEPENDENCE OF WELL PRODUCTIVITY ON FRACTURE WETTABILITY To determine the dependence of well productivity on the wettability of the frac sand, it is necessary to know, first, the effect of fracture wettability on fracture permeability and, second, the effect of fracture permeability on well productivity. The relationship of these variables is considered separately in the order indicated. Effect of Wettability on Permeability Fig. 1 shows relative permeability relations for 20-30 mesh Ottawa sand. Inspection of these curves reveals that the relative permeability to oil when a small amount of water accompanies the flow is considerably higher when water rather than oil is the wetting phase. For

By L. Yarborough, L. R. Smith

This paper presents results of a laboratory study of retrograde condensate recovery by revaporization into dry injection gas. Flow tests were performed in 10.6-ft long sand packs at 100F and 1,500 psi. In three runs methane revaporized the liquid from a n-pentane-methane mixture in the presence of immobile water. TWO of these tests were water-wet, and the third was totally oil-wet. In the three runs n-pentane recovery was complete after 2.5 hydrocarbon PV of injection. There was no significant performance difference between the two wettability extremes. In a fourth experiment, a methane-hydrogen sulfide mixture revaporized a synthetic light, sour condensate. No water saturation was present. Equilibrium compositions and volumetric data were obtained for the four-component condensate. The heavy component, n-beptane, was removed after 6 PV production. Comparison of the effluent fluid compositions with known equilibrium data shows that the flowing fluid was equilibrium vapor and that the mixing zone between equilibrium vapor and dry injection gas was short. Data indicated that complete recovery of retrograde liquid occurred after it was contacted by a sufficient quantity of dry gas. INTRODUCTION When pressure declines below the fluid dew point in a gas condensate reservoir, a liquid phase forms. In this process, referred to as retrograde condensation, the quantity of liquid formed is frequently small enough that the liquid is not a flowing phase. To prevent loss of valuable retrograde liquids, the process of dry gas cycling has been employed for several years as a more or less standard practice. In this procedure the reservoir pressure is maintained above the fluid dew point so that the liquid components may be produced as vapor and then separated at the surface. Although full pressure maintenance by gas cycling seems ideal in terms of preventing liquids loss, several factors can reduce the atuactiveness of such an operation. From a study of a condensate reservoir in Alberta, Canada, Havlena et a1.1 con-cluded that cycling under conditions of declining pressure leads to economic advantages and to a high recovery of hydrocarbon liquids. This study considered effects of volumetric sweep efficiency, retrograde behavior of the original wet gas and revaporization characteristics of the retrograde liquid when contacted by dry gas. The first major work concerning revaporization of liquid in a gas condensate system is that of Standing et a1.2 Calculations based upon the PVT behavior of a recombined gas condensate fluid indicated that all retrograde liquid can be recovered if it is contacted by a sufficient quantity of dry gas. The paper considered the effect of variable permeability upon the recovery of retrograde liquid. Standing et al. concluded that recovery of heavier components in the retrograde liquid is greatest if reservoir pressure is allowed to decline below the dew point prior to dry gas injection. Since the work of Standing et al., several laboratory studies have been reported which show that recovery of hydrocarbon liquids by vaporization into dry injected gas can contribute to increased recovery above that obtained by ordinary production practices. Vaporization from retrograde condensate,3 conventional oil4-7 and volatile oil8 reservoirs has been considered. There is little work that deals with revaporization recovery from condensate reservoirs. This study demonstrates that vapor-liquid equilibrium exists when a dry gas is injected into a porous medium containing retrograde condensate; investigates the effect of wettability on revaporization of retrograde condensate; and provides an indication of the amount of dry gas necessary to

Jan 1, 1969

By F. H. Bunge, W. H. Jr. Dailey

This paper covers an investigation of the magnetic roasting characteristics of several iron ores when treated in the form of small pebbles (1/8" to 1/2" in size), and in the form of balled fines. The roasting treatment was carried out with apparatus capable of very close control of time, temperature, face velocity, and per cent combustible in the reaction gas. The effect of rapid initial heating was not studied although it is believed that this has a major effect on the results when processing solid pebbles. The test equipment is a fixed bed type, with such a wide range of gas velocities, temperature, combustible content and etc., that the results obtained can be made to approximate those from various commercial roasting processes. The data presented in this report covers reaction rates, effect of processing variables on silica in the concentrate, flow resistance of beds, and to a limited extent, the effect of particle size. The work is far from complete and raises many more problems than it gives answers for. We believe, however, that much of the information will be useful to those engaged in investigation of magnetic roasting processes. We measured the time required for various degrees of completion of the reaction of hematite to magnetite, for finely pound material in balled form and for carefully sized crushed ore. Measurements were made for a variety of Minnesota and Labrador ores. This report covers an ore requiring fine ginding (-325 M) for liberation (Lower Kevin) and an ore requiring coarser grinding (-100 M) for liberation (Upper Olson). These ores represent approximately the range of characteristics for a group in the west end of the Mesabi Range. Our data shows that the reaction rate is very fast for the finely ground material and that tests are readily reproducible. The reaction rate of the larger size material, in the range of 1/8" to 1/2", is much slower and the results more erratic. We found that for the ores tested, the percentage of silica in the Davis tube magnetic concentrate was a function of iron recovery. Normally the concentrate had a low and relatively uniform percentage of silica up to a critical value of recovery. Above this critical recovery value the percentage of silica increased very rapidly. For example, for one particular ore roasted in the form of 3/8" diameter balls made from -28 mesh fines, the silica remained at about 7% to 8% until the recovery exceeded about 93%. Increasing the recovery beyond 93% resulted in over 25% silica with the additional recovery. The degree of conversion of hematite to magnetite (% completion of roast) required to obtain 93% recovery for balled material, varied inversely with the gas flow rate. Percentage silica in the concentrate resulting from roasting 3/16" and 1/2" solid material was relatively erratic. However, for varying degrees of iron recovery the lowest silica percentages corresponded to those obtainable when roasting fines. It is thought the probable reason for the erratic values was the variation in shattering or cracking of the pebbles during initial heating and roasting. There is some indication that very fast initial heating will greatly increase the permeability of the individual particles of ore to gas flow so that the reaction rate for coarse sizes will approach that obtainable with balled fine material.

Jan 1, 1961

By A. J. Teplitz, R. J. Goodwin

A new type water shut-off for use in air drilling has been developed. The method has been 99 to 100 per rent effective in several different formations of inter-ranular-type porosity. Since costs for materials, time and equipment used are relatively small, the process should extend economies of air drilling to many new areas. The treatment involves a new technique for forming a water-inroluble precipitate within the pores of a rock. Advantage it taken of the difference in mobility of a liquid and a gas in porous media to achieve the greatest volume of precipitate in a given pore. Reactants selected for the laboratory (2nd field tests were aluminum sulfate solution and gaseous ammonia. This process has been tested in both intergranular and fractured-type porosities. It has consistently shut-of between 99 and 100 per cent of the water flowing from formations having intergranular-type porosity and perrlreuhilities ranging from a few millidarcise to over a darcy The treatment is not particularly suitable for shutting-off water from fractured formations although plugging of the order of 50 per cent or greater has been achieved in all such applications. Among advantages of the treatment are: (I) no reaction waiting rime after a relatively short placement time, (2) a low mate-rials cost of about $3/f1 of hole treated, (3) use of common service-type equipment for treatment, and (4) no unusual requirements for mixing and placement. INTRODUCTION In rotary drilling with air or gas it has been possible to increase bit life by tenfold and more than double rate of penetration over corresponding performance when drilling with mud. These factors have amounted to as much as 22 per cent savings on total cost of drilling a well. However, these advantages are rapidly lost when water is encountered in an air- or gas-drilled well because water interferes with the removal of cuttings from the hole and also gives rise to other difficulties. In attempting to combat water troubles, operators have commonly resorted to such measures as mist drilling, treatment with cement or chemicals, converting to conventional mud drilling, or setting casing. In many cases these measures have either been costly or ineffective. In an effort to overcome this problem, studies were undertaken to develop an effective and economical water shut-off technique for use in formations possessing inter-granular-type porosity. Extensive laboratory experimentation finally led to a unique method for producing a water-insoluble precipitate within the pores of a sandstone. The unique part of the treatment is use of a liquid and a gas to form the precipitate, and in this case the reactants used were aluminum sulfate solution and gaseous ammonia. The reaction between these two materials is shown in the following equation. Al2 (SO1)3 - 18 H20 6NH2? saturated Water- Solution Cat 2A1(OH)3 . n H20 3(NH4)2SO • n H20 Solid Solid That is, a solid precipitate consisting of aluminum hydroxide and ammonium sulfate is formed when ammonia reacts with aqueous aluminum sulfate. The aluminum hydroxide is insoluble in water and the ammonium sulfate, though soluble, can only be removed from the formation pores by diffusion—an extremely slow process. Although the precipitate formed by the reaction is not particularly firm, great strength is not needed for a precipitate to bridge and plug intergran-ular-type porosity. A flow path in such a system is extremely tortuous and involves a great variety of pore

By C. C. Mattax, J. E. Bobek, M. O. Denekas

ABSTRACT investigations in recent years have shown that rock wettability can exert a profound influence on the displacement of oil by water from oil producing reservoirs. Core analyses frequently show oil recoveries from preferentially water-wet rock to be significantly greater than those from preferentially oil-wet rock. Thus, an accurate prediction of water-drive or waterflood oil recovery is dependent on the evaluation of reservoir rock wettability. Laboratory and field studies have been undertaken to examine and develop methods which may be used to measure rock wettahililiy, to investigate factors which may alter the wettability of reservoir rock, and to determine the wettability of specific reservoirs. It has been found that measurement of the rate and volume of spontaneous imbibition of the wet-ting phase by a rock is a reliable and reproducible test for semi-quantitarive determination of preferential rock wettability. Laboratory tests have shown that the wettability of reservoir rock may depend on both the crude oil composition and the rock type. Field and laboratory tests have indicated that coring flulids and core handling techniques can cause significant changes in the wettability of rock surfaces. However, a few fluids, brine in particular, appear not to affect core wettability and may be used when coring to determine reservoir wettability. Core handling and packing procedures have been developed which preserve core wettability during storage and laboratory testing. The wetfability characteristics of six reservoirs have been evaluated by wettabilify tests performed in the field on fresh cores cut with brine or special water-base muds. The tests indicated that all six reservoirs are water wet; however, the de-gree differed from one reservoir to another. INTRODUCTION Although surface properties of reservoir rock and interfacial characteristics of rock, crude oil, and water systems have been discussed for many years, the full significance of these properties to the production of oil is still in the process of evaluation. It is known, however, that one surface characteristic—preferential wettability of the reservoir rock—-is of paramount importance when the reservoir is being produced by water-flood or water-drive mechanisms. The importance of rock wettability has been pointed out by several authors'.',%* who have found that pref- erentially water-wet cores flood more efficiently than oil-wet cores; that is, more oil is recovered from water-wet cores in the early flooding stages than from oil-wet cores. Other authors'," indicate that waterflood oil recovery from cores of intermediate wettability may be greater than that from either strongly water-wet or strongly oil-wet cores. These recent investigations emphasize that the true wettability of a reservoir must be known before the performance of waterflood or water-drive reservoirs can be accurately evaluated. When reservoir wettability is to be determined by core analysis, precautions must be taken to maintain the original wettability which can be altered readily during coring5 nd testing.' In the coring operation the core may be partially or completely penetrated by the drilling fluid which, if it contains surface active materials, may drastically change the wettability of the core. Also, improper core handling during stcrage and testing may change its wettability because of evaporation of fluids or exposure to oxygen or surface active contaminants. One purpose of this paper is to discuss methods for obtaining, preserving, and testing cores without altering their original wettability. In addition, the results of wettability tests on fresh and preserved cores from six reservoirs are presented where special precautions were taken to obtain samples without altering their wettability during the coring operation.

By L. W. Pommier, F. B. Brien, A. K. Bhasin

The diflerential movement of solid particles through solid-liquid suspensions is very important to many branches of engineering. The flow of suspensions around immersed bodies is mainly of a turbulent nature. Problems are encountered when attempts are made, as is the general practice, to extrapolate the velocity and resistance relationships of Newton, pertaining to Newtonian systems, into non-Newtonian solid-liquid suspensions. The conventional velocity and resistance relationships for turbulent flow in fluids when applied to suspensions, do not take into consideration the two very important variables: suspension particle size and solid volume fraction. A study of the effect of suspension particle size (dgb) on the velocity of falling balls leads to the concept of a critical particle size (dgc) at which the suspensions will be Newtonian. This leads to the classification of static suspensions into two types: suspensions consisting of particle of diameter dgh > dgt, and those with dgh, < dgr. Separate velocity and resistance equations for these two types of suspensions have been proposed, taking into account both the solid particle size and solid volume fraction. The agreement between the velocities predicted from the proposed equations and the measured velocities, confirms their validity. The resistance force offered by suspensions to the movement of immersed bodies has been calculated from the proposed equations, and the effects of suspension particle size and solid volume fraction on the resistance force and velocity have been examined. The movement of immersed bodies in solid-liquid suspensions is of great importance in many areas of engineering such as minerals processing, oil well drilling, suspension flow in pipelines, and hydrometallurgy. A number of mineral dressing processes deal essentially with the movement of solids in suspensions—in particular, classification, thickening, filtration, ore washing, and gravity concentration—thus a study of the fluid characteristics of suspensions is of theoretical and practical interest.&apos; A rigorous analysis of the mechanisms of momentum transport of a solid-liquid system is complex indeed. The rheological properties of the suspensions deviate from those of liquids, varying, for example, with density, solid volume fraction, size and shape of the solid phase of the suspension, and with the density and viscosity of the liquid phase. The flow of suspensions around immersed bodies is mainly of a turbulent nature and hence studies of the turbulent flow characteristics of suspensions are of par- ticular importance. Problems are encountered when attempts are made to extrapolate the velocity and resistance relationships of Newton, pertaining to Newtonian systems, into non-Newtonian solid-liquid suspensions. Due to the numerous variables present in a suspension, certain limitations and assumptions become necessary in order to produce quantitative relationships for predicting their effects. The solid particle size and the solid volume fraction are two of the more important variables. By comparing the measured and calculated Newtonian velocities of falling balls in simple static suspensions, the existing velocity and resistance relationships have been modified to take these variables into account. In order to keep the study less complex, all other variables such as the characteristics of suspending liquid and shape of the particle are maintained constant. Objective The objective of the present investigation is to modify the Newtonian velocity and resistance equations in order to take into account the suspension particle size and solid volume fraction. Theory Liquids are classified on the basis of viscosity, which may be defined as the relationship between applied shear stress and resulting rate of shear.&apos; pure single-phase fluids composed of small light molecules behave as Newtonian liquids, having a single viscosity pa-

Jan 1, 1971

By M. P. Tixier, F. Segesman

Explanations bused on theory and laboratory tests tire offered for certain unusual features of SP logs which may befog their interpretation, namely the "sawtooth" SP and the reduction or increase of SP with time. The sawtooth SP is frequently seen in SP recordings of thick, very permeable watcr. sands of the Louisiana Gulf Coast. Using SP data from a resistor network analog, this anomaly is explained on the basis of a thin shale streak within the sand. under which the invading filtrate accumulates by gravity segregcitiorr. The electromotive force then appearing across the shale streak gives rise to the anomalous SP. Reduction of the SP on successive logging runs Ira often been observed in very permeable sands when as indicated by the resistivity curves, the invasion depth has been reduced to practically zero. Laboratory results verify that this phenomenon may be due, to the presence of air electromotive force, across the mod rake when the fluids on either side differ in activity. Also, there is, in some cases; an increase of SP deflection on successive logging runs, because the emf initially present across the mud cake disappears as the somewhat saline water just behind the mud cake is progressively flushed out by the invading filtrate.. Field example and laboratory data are presented. I N T R ODUCT1ON Some unusual features are frequently observed on certain SP logs which make interpretation difficult. The purpose of this paper is to offer explanations of several cases of interest. All of these arc related to the conditions of invasion. The cases to be discussed are as follows. 1. The sawtooth SP anomaly which is frequently seen within the thick, highly permeable saltwater sands of the Louisiuana Gulf Coast 1. Reduction of the SP deflection from the usual sand line in very permeable sections when the depth of invasion is practically nil. As will be explained, such a reduction is attributable to a membrane electromotive force across the mud cake. 3. An increase of the SP with time just after the iormation is drilled as a result of progressive flushing of the invaded zone. FUNDAMENTALS OF SP PHENOMENA An explanation of SP phenomena must begin with the following basic ideas. 1. The SP log derives its character from ohmic potential differences in the hole produced by currents flowing through the mud.&apos; These currents are driven by electromotive forces which are primarily electrochemical in origin. Other possible types of SP-producing electromotive forces may be disregarded for the purposes of this paper. 2. The electrochemical emf&apos;s associated with permeable formations are now understood to consist of liquid-junction emf&apos;s and membrane emf&apos;s.&apos;,&apos; As schematically shown by thc battery symbols in Fig. 1, the liquid-junction emf, E,,,, exists at the contact between waters of different chemical activities, a,,,, (mud filtrate) and tr,,. (formation water); the shale membrane emf, lS.sn. exists across the adjacent shales whcn they separate waters of different activities. The emf&apos;s just cited are additivc in producing SP currents (arrowed circles of Fig. I). Thus, neglecting for the moment any possible membrane emf across thc mud cake, the total electrochemical emf, E,, will be given by their sum, where K,., -! K,q,, = 12 + 59, or 71 at 75 °F. In the log interpretations the SP of a thick sand (i.e.. the static SP) is generally related to the activities of the filtrate and formation water through Eq. 1. by setting the static SP equal to - E,.

By A. M. Sarem, J. M. Campbell

Molecular refraction is introduced as a new and improved third parameter for prediction of the PVT behavior of hydrocarbon systems. This parameter, characterizing the complex as well as the pure hydrocarbon systems (1) is a direct measure of London dispersion forces which affect the PVT behavior; (2) can be measured directly, accurately and easily for complex as well as pure hydrocarbon systems; (3) varies significantly between the reference substances thus allowing accurate interpolation of PVT properties; and (4) has a fundamentally sound basis. Molal average molecular refraction was used with the pseudocritical mixing rule proposed by Leland and Mueller to predict the molal volume of liquid and vapor for 84 published data points on nC4-nCI0, Cl-nC5, Cl-nC4-nC10 systems in the region of coexisting vapor-liquid and at the critical point. The same technique was applied to predict the densities of liquid hydrocarbon mixtures in the two-phase and single-phase regions near the critical point for seven different systems each having different properties of the heptanes-plus fraction, but all simulating the fluids of either gas-condensate or volatile oil reservoirs. A modification of the Leland-Mueller mixing rule for the determination of pseudocritical properties is also presented which yields more accurate liquid density predictions than the original form when used with the proposed third parameter. INTRODUCTION The PVT behavior of multicomponent systems has received widespread attention in the literature in recent years. A large portion of the reported work has stemmed from attempts to overcome the inherent difficulties encountered when using the standard compressibility-factor chart which shows 2 as a function of reduced temperature T, and and reduced pressure p,. This chart assumes that z, is constant for all systems. The error in this assumption is not pronounced for pipeline-type gases high in methane and low in heavy ends, particularly when contained at moderate pressures. For such gases the error in the calculated z is usually less than 2 to 3 per cent. However, the reliability of this approach becomes somewhat nebulous for gas condensate and volatile oil systems at high pressure. One logical approach has been to recognize the variation of 2,. This idea was first suggested by Meissner and Seferianl and used by Lyderson, Greenkorn and Hougen2 to prepare extensive tables of thermodynamic properties. Other third parameters have been proposed by Stockmeyer, Kihara, Riedel, Lightfoot, Bloomer and Pitzer. These were tested by Satter and Campbel13 for many gas mixtures and it was shown that they were inter-related. All of these third parameters have a common fault — they cannot be directly evaluated for the heptanes-plus fraction. Consequently, one necessary requisite of an improved method for predicting the density of multicomponent hydrocarbon systems, was development of a third parameter that could be evaluated for that fraction. PREVIOUS MULTICOMPONENT DENSITY PREDICTION METHODS Sage and Lacey4 suggested a method of using partial molal volumes for computing the density of hydrocarbon gas mixture for pressures to 3,000 psi. In this technique, they approximate the complex multicomponent gaseous mixtures by a quarternary system of methane, ethane, propane and butane. Sage, Hicks and Lacey5 suggest a method of using partial molal volumes for computing the density of hydrocarbon liquids. The results agree within 3 per cent of the experimental values. However, the composition range is limited to about 10 per cent by weight of methane. Consequently, this correlation does not cover the low-molecular-weight liquid similar to natural gasoline and high-pressure gas condensates.

Jan 1, 1966

By Roland de Wit

Conclusions reached in a paper by weertmanl are amplified in a mathematical and graphical way. It is shown that in a stressed crystal a straight dis-location may be in a position of unstable equilibrium with respect to helix development, and how a small perturbation may start the dislocation off on its helical path. Helix development occurs by diffision; bulk diffusion is necessary for development from a screw, but core diffision is sufficient for development from an edge dislocation. For a mixed dislocation helix development can take place by core diffusion if the helix also climbs; a diffusion reversal takes place when the slope of the helix equals the slope of the Burgers vector. The work done on a crystal by the external forces is graphically shown to be consistent with the direction of motion of the dislocation in helix development. Finally a detailed mechanism for tangle formation from helices is presented. In the course of helix development a glide situation may be reached where a segment of each helix loop lies in a slip plane in which it can expand by glide. Thus is it visualized how a helix can deteriorate into a tangle. A paper by weertmanl proposes dislocation-tangle formation by a helical dislocation mechanism. The present paper amplifies Weertman&apos;s arguments in a mathematical and graphical way and presents some further ramifications of the proposed model. The importance of dislocation tangles is discussed in Weertman&apos;s paper and the references cited therein. The mechanism of their formation is not yet understood. Weertman proposes that in cold-worked crystals conditions exist suitable for the conversion of straight dislocations into helices and subsequently into tangles. Helix formation occurs by a diffusion process and Weertman proposes that at low temperatures only core diffusion is important. The present paper necessarily repeats some of Weertman&apos;s work. Since the mathematical development and notation used are slightly different from his, this was thought necessary for clarity. GEOMETRY OF THE HELIX weertman2 has shown that the equilibrium form of any dislocation line is a helix if it is assumed that the energy per unit length (line tension) of the dis- location is constant. For the special case that no external forces act on the dislocation, the helix reduces to a straight line. We shall assume in this paper that the dislocation has a helical form even when it is not in equilibrium. The parametric equation of a helix is, see Fig. l: where a is the radius of the cylinder tangent to the helix, and 270 the pitch of the helix. The pitch is related to v, the number of turns per unit length (along the axis) by the relation: When a = 0 Eq. [I] gives a straight line in the z direction. The growth of a straight dislocation into a helix is now described mathematically by letting a vary from zero to its final value. The tangent to the helix is given by where is the path length along the helix. This gives the direction of t and since its magnitude is unity we must have So that dcp/ds = (a2 +p2)-"&apos;. The curvature of the helix is given by where n = -(cos + sin) is a unit vector normal to the helix. Note that the vectors k and n always point toward the axis of the helix, Fig. 1. FORCE ON THE HELIX The external force which makes the straight dis-

Jan 1, 1963

By K. E. Gray, M. S. Seth

Equations of elasticity for transversely isotropic, axisymmetric, homogeneous, porous media exhibiting pore fluid pressure were formulated. Using an analogy between thermal and porous body stresses, it was shown that the solution for a transversely isotropic porous body may be obtained by incorporating body forces and the stresses due to a boundary load into the corresponding solution for the thermal stress problem. Equations of elasticity ad the thermal analogy method were used to determine transient horizontal, tangential, and vertical stresses and radial displacement in a semi-infinite cylindrical region when either a constant pressure or a constant rate of flow is maintained at the wellbore. The vertical and tangential displacements are zero from the conditions of the problem. A numerical analysis was made of the solutions obtained by using a digital computer to determine the relative influence of each system variable. Considering rock as a porous body with internal fluid pressure generally gives results significantly different than considering the rock to be nonporous; the directional character of rocks leads to significant differences as compared to results based upon the common assumption of isotropy. Stress gradients are high near the wellbore but die out away from the well. Radial stresses are compressive or neutral, whereas tangential stresses are tensile, neutral or compressive, depending upon the boundary conditions and physical properties of the system Vertical stresses are compressive for an unbounded system. For constant wellbore injection rate, the vertical stress is proportional to the rate of fluid injection and decreases with time, whereas the radial and tangential stresses increase with time. At a given location, the radial displacement generally is very dependent upon time. INTRODUCTION A realistic appraisal of the state of stress in subsurface rock formations would be of considerable interest and use to the petroleum industry. For example, knowing the state of stress in proximity to a wellbore would be of fundamental importance in designing a fracturing operation or, more important, of clearly understanding the conditions necessary to produce rock failure of desired dimensions and geometry. Understanding conditions necessary for rock failure at the wellbore would also be of utility in a preventive sense. For example, borehole stability is an important consideration for many rock formations, and knowledge of the stress state at and near the wellbore under conditions of substantial pressure gradient due to fluid flow would be of great value. When fluid flows through a porous body which is initially at some uniform stress level, the following forces generate stresses at any point in the body. (1) Forces due to nonuniform pressure distribution. With increasing pressure the elements of a body are compressed. Such compression cannot proceed freely in a continuum when the pressure is not uniform throughout, and thus, stresses due to flow of fluid are set up. (2) Pore fluid pressure. This gives rise to normal stresses whose value at any point is the product of areal porosity and the fluid pressure. Although the fluid exerts uniform pressure, the stresses it creates in an anisotropic body may not be the same in all directions since the areal porosity in an anisotropic porous body is a direction-dependent quantity. This consideration leads to the concept of directional porosity. (3) Body Forces. The flow of the moving fluid imparts a force to the rock matrix, the magnitude of which depends upon the pressure

Jan 1, 1969

By Frank Woolley, John F. Elliott

The high-temperatzrre solulion calorimeter has been modified and an extension dynamic analysis of i/s transient behavior has provided an improved basis for interpretation of the experimental data. The partial molar heats of mixing, Him, of aluminum, copper, and silicon in the corresponding binary liquid-iron alloys haz,e been measured directly at 1600°C. The resulls in kcal per g-alom are: THE high-temperature1,2 solution calorimeter was planned and designed to obtain directly the partial molar heat of solution of solute elements in a variety of liquid metals that might serve as solvents. Results obtained in the temperature range of 1000° to 1200°C were described in the two earlier publications. However, a long-term goal in the program has been to obtain measurements at 1600°C of the heats of solution of elements in liquid iron. Hence, subsequent to the work last reported,2 and based on the experience of the first two studies, the calorimeter system has been modified and operated at 1600°C to obtain measurements on the Fe-Si, Fe-A1, and Fe-Cu systems. This paper reports the results of the work. THE MODIFIED SYSTEM It was clear from the earlier results that the most precise measurements can be obtained with the high-temperature solution calorimeter when the solution time is less than approximately 30 sec. This can be achieved only when the bath temperature, Tb, is above the melting (liquidus) temperature of the solute material being dropped. A second point of importance is that the refractories used earlier liberated considerable water so that, although the oxygen potential of the atmosphere in the system was satisfactory for work with nickel and copper, it was too high for work with iron, silicon, and so forth. Third, for work at 1550" to 1650°C, an improved temperature-sensing unit is needed. The modified calorimeter in its latest form is shown schematically in Fig. 1. The refractory brick and the Kanthal-Super heating elements which formed the furnace for heating the solute addition have been replaced by a smaller resistance-heated tube furnace which is insulated with bubble-grain alumina. A more elaborate gas purification system was installed to maintain a satisfactorily low oxygen potential in the atmosphere of the calorinieter chamber and of the solute addition furnace. As was the case in the earlier work, at the beginning of a run the calorimeter chamber is evacuated and then filled with purified argon so that a total pressure slightly in excess of 1 atm is maintained during the run. When either of the furnaces within the enclosure attains a red heat, 6 pct H2 is added to the atmosphere. Throughout the run, gas from the calorimeter is circulated through a de-oxidation system at the rate of approximately 5 standard liters per min; the changeover time for the gas within the calorimeter enclosure is approximately 1 hr. The essential stages of the deoxidation system are: a copper furnace at 600°C, a drying tube of anhydrite, and a titanium furnace at 800°C. The oxygen potential of the gas stream in the purification system can be monitored at several points by a stabilized zirconia oxygen cell. This cell is invaluable in detecting the development of leaks in the container vessel and the gas circulating system. The installation of the solute-addition furnace allowed either of two types of temperature-sensing units to be mounted on a water-cooled probe. The first was a small optical device using a silicon diode that was

Jan 1, 1968

By J. E. Campbell, A. W. Wesner, M. Pobereskin

This paper summarizes the results of an investigation sponsored by The Coates Steel Products Company. The objective was to determine the relative effects of certain chemical and physical properties on the wear resistance of grinding balls when grinding cement. In making this study, a number of types of balls were used in both dry and wet grinding in commercial ball mills. The radioactive-tracer technique was used in separating the test balls from the rest of the mill charge and in sorting the different types of halls that were all tested at the same time for each of the grinding operations. PROCESSING OF GRINDING BALLS In order to determine whether the properties of grinding balls, namely, composition, microstructure and hardness, can be related to the rate of wear, the halls used in this study were selected to represent various combinations of these properties. It was recognized that the mechanism of wear was not the same in the wet mill as in the dry mill. Therefore, the types of balls tested in each of the two environments were not necessarily the same. However, all of the types of balls evaluated in the dry mill were tested simultaneously for one time period, while those evaluated in the wet mill were tested simultaneously for three different time periods. All of the test balls were separated from the charge when the mill was dumped. All of the balls were of 0.940-inch diameter when charged, and all but the regular production balls were finish ground to this size to eliminate the decarburized surface layers. The steels and processing methods used, as well as the micro-structures and hardness levels of the balls, are described as follows: Regular production forged SAE 1095 steel balls were used in both the wet and dry mills. They were forged to a nominal diameter of 0.940 inch and quenched in oil from the forging temperature. Each retained a partially decarburized surface layer from the forging bar stock; the maximum depth of this layer was about 0.030 inch and the decarburization was negligible where the ball was sheared from the bar. The hardness at the surface was 40 to 46 Rock-well C in the partially decarburized area and 57 to 62 Rockwell C in the areas not decarburized. The hardened zone extended to a depth of about one-third of the radius. Below the decarburized layer, the hardened zone consisted primarily of hard as-quenched martensite with varying amounts of retained austenite. This structure changed to fine pearlite at a depth of about one-third of the radius. In order to eliminate the effect of the decarburized layer, a set of production balls of SAE 1095 steel was forged to about a 1-inch diameter, quenched in oil from the forging temperature, and ground on ball-bearing grinding equipment to a 0.940-inch diameter to remove the decarburized layer. The balls&apos; hardened zones were similar to those in the previous set. The hardness of the finished surfaces was 52 to 60 Rockwell C. A slight amount of decarburization apparently remained after the removal of about 0.030 inch from the surface. Balls of this type were tested in the dry mill only. Another set of forged SAE 1095 steel balls of 1-inch diameter was heated to 1500 F and quenched

Jan 1, 1961

By Alan Stanley

The MacIntyre Development of the National Lead Co. is located at Tahawus, N. Y. The operations involve the mining and concentrating of a titaniferous iron ore to produce an ilmenite concentrate and a magnetite concentrate. Construction of the MacIntyre plant was commenced during the summer of 1941, when world conditions threatened to cut off the supply of Indian ilmenite. An open pit mining operation was developed and the crushing and milling equipment put in operation in July 1942. A general description of the operation was given in the Adirondack Issue of Mining and Metallurgy for November 1943. The metallurgy of the mill operation was described by Mr. Frank R. Milliken,* Plant Manager, National Lead Company, MacIntyre Development, and presented at the AIME New York Meeting, February 1948.

Jan 1, 1949

By Harvey S. Mudd

WHEN talking about Europe it is well to endeavor to keep politics and economics apart but they have become so intermingled in recent years that the discussion of one topic inevitably leads to the other. Economic influences formerly prevailed over politics but today national and international economies are governed by political forces. Commerce in raw materials, food, and manufactured products is now so restricted by governmental controls that the capacity of the world to produce and to consume, to exchange goods and to pay for them, cannot be gauged by the past or predicted by a multitude of experts. In prewar days there were some yardsticks but today there are none. Thus it is hazardous to make forecasts, for in all fields of human effort the world has been cast upon an uncharted sea.

Jan 1, 1947

By H. W. Gillett

BATTELLE Memorial Institute is an endowed in stitution for scientific research in metallurgy, fuels, and allied fields, established by the will of Gordon Battelle, 2nd, as a memorial to his father, Colonel John Gordon Battelle. Before I tell you more of what Battelle Memorial Institute is, I want to go back a bit and tell you why it is. Colonel Battelle began his services in the iron and steel industry in Wheeling in 1866 and in 1883 came to Ohio, where he successively engaged in the iron and steel industry in Cincinnati, Piqua and Columbus. The family had been prominent in Ohio affairs since 1788, when Gordon Battelle&apos;s great-great-grandfather came from New England to settle in Marietta. He was one of the pioneers and a member of the famous "Ohio Company."

Jan 1, 1929

By Andrews Allen

WE all remember when, a few years ago the preparation of coal was nothing but a matter of having somebody at the face or somebody in the railroad car pick out the impurities; also the sizes were generally&apos; made" over a bar screen. Anything that was black was coal; and the only matecia1 picked out was the slate or rock-impurities that could be distinguished by eye or by hefting. This was all right as long. & coal could be sold at. a good price. After all, we are all in business to -make the most money honestly out of a certain acreage of coal and a certain plant. For this purpose what is required is the greatest possible recovery of marketable coal and the highest market price.

Jan 1, 1929

By Lewis Carroll

AS he contemplates the numerous good things the hard-working committees have evolved for the 140th Meeting of the Institute, the Editor knows just how the walrus felt when he uttered his memorable, if somewhat lugubrious lines. For there are the Annual Reception and Dinner at the Commodore, &apos;the Gold Supply Symposium, the luncheons, general and special, and the Annual Institute of Metals Lecture, a Round Table on Iron Ore and a wonderful Informal Dance at the Grand Central Art, Gallery, substantial general sessions, a Smoker-and many other things. -Old, friends and new, reminiscences and confidential chats, horizons pushed back by new information and adjusted perspectives, courage revived and ambitions stimulated-one with a flair for the modernistic might make something-or nothing-of the kaleidoscopic preview &apos;of the coming Annual Meeting.

Jan 1, 1931