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By James O. Lewis

Gravity drainage is the self-propulsion of oil downward in the reservoir rock. Under favorable natural and operational conditions, it has been found to effect recoveries comparable to water displacement. With modern technical knowledge, the operator can often make a choice between dissolved gas drive, water drive and gravity drainage as the principal recovery agent in a reservoir. It is desirable that the opeator be able to determine which of the three agents will be most effective under each set of conditions. So far, gravity drainage has received less consideration than the other two. In this paper. an endeavor is made to set forth some of the principles of gravity drainage, to point out the types of reservoirs favorable for it, and to show how it may be applied in them. Field examples are described and discussed. Introduction Since early in the history of the oil industry, it has been recognized that gravity is one of the three important natural forces for expelling oil from the reservoir rock. As knowledge of the technology of oil recovery progressed, ideas changed with respect to the relative importance of the three forces and with respect to the manners in which they functioned. For a time, disproportionate emphasis was placed on the importance and function of gas and the need for conserving gas pressures. More recently, disproportionate emphasis has been placed on encroaching edge water. Only lately has there been evidence that the function and importance of gravity was to receive due consideration. Study of this neglected phase of oil recovery is needed to round out our knowledge of reservoir behaviors and to gain a balanced viewpoint of the interplay of forces that may operate in varying importance in reservoirs. The purpose of this paper is to discuss mainly in a qualitative way, the functions of gravity, to present some concrete instances where it has been important and to raise some questions that should be investigated further. Oil-recovery Agents The important natural agents for effecting oil recovery that may be originally available in a reservoir are gas, both dissolved in the oil and free in gas caps, encroaching edge water and gravity. Each of these agents can act in a dual capacity—physically to overcome the surface energies that hold the oil within the pores and mechanically to overcome viscous . resistance and to propel the oil through the porous reservoir rock to the wells. Advancing edge water displaces the oil from the pores and lifts it updip to structurally lower wells. Gravity drains the oil from the pores and flows it downdip to the wells. Gas displaces oil from the pores, entrains it in the gas stream and flows it to the wells, but gas in solution also affects the physical properties of the oil and thus can influence oil recovery by the other agents, whether or not the mechanical energy in the gas is utilized. Of the two functions of these agents, the more important is the ability to dis-

Jan 1, 1944

By James O. Lewis

Gravity drainage is the self-propulsion of oil downward in the reservoir rock. Under favorable natural and operational conditions, it has been found to effect recoveries comparable to water displacement. With modern technical knowledge, the operator can often make a choice between dissolved gas drive, water drive and gravity drainage as the principal recovery agent in a reservoir. It is desirable that the opeator be able to determine which of the three agents will be most effective under each set of conditions. So far, gravity drainage has received less consideration than the other two. In this paper. an endeavor is made to set forth some of the principles of gravity drainage, to point out the types of reservoirs favorable for it, and to show how it may be applied in them. Field examples are described and discussed. Introduction Since early in the history of the oil industry, it has been recognized that gravity is one of the three important natural forces for expelling oil from the reservoir rock. As knowledge of the technology of oil recovery progressed, ideas changed with respect to the relative importance of the three forces and with respect to the manners in which they functioned. For a time, disproportionate emphasis was placed on the importance and function of gas and the need for conserving gas pressures. More recently, disproportionate emphasis has been placed on encroaching edge water. Only lately has there been evidence that the function and importance of gravity was to receive due consideration. Study of this neglected phase of oil recovery is needed to round out our knowledge of reservoir behaviors and to gain a balanced viewpoint of the interplay of forces that may operate in varying importance in reservoirs. The purpose of this paper is to discuss mainly in a qualitative way, the functions of gravity, to present some concrete instances where it has been important and to raise some questions that should be investigated further. Oil-recovery Agents The important natural agents for effecting oil recovery that may be originally available in a reservoir are gas, both dissolved in the oil and free in gas caps, encroaching edge water and gravity. Each of these agents can act in a dual capacity—physically to overcome the surface energies that hold the oil within the pores and mechanically to overcome viscous . resistance and to propel the oil through the porous reservoir rock to the wells. Advancing edge water displaces the oil from the pores and lifts it updip to structurally lower wells. Gravity drains the oil from the pores and flows it downdip to the wells. Gas displaces oil from the pores, entrains it in the gas stream and flows it to the wells, but gas in solution also affects the physical properties of the oil and thus can influence oil recovery by the other agents, whether or not the mechanical energy in the gas is utilized. Of the two functions of these agents, the more important is the ability to dis-

Jan 1, 1944

By John Jermain Porter

THe value of any particular ore, coke, or limestone, for iron-making, depends upon its effect, first, upon the quality or value of the resultant product; and second, upon the cost of smelting. The factors under the first head are the percentages of phosphorus, manganese, and other elements, which remain in the pig-iron ; while those under the second head are the percentages of iron, carbon, or lime, the slag-forming constituents, which must be fluxed, and any other ingredients which give rise to variations in cost of fuel and flux. The first of these criteria of value is perhaps not capable of being reduced to a general formula embracing all cases, since it must vary to a great extent with market-fluctuations. For example, Bessemer pig is worth sometimes more and sometimes less than foundry-pig; and the premium paid for high manganese varies within wide limits. The second, or smelt-ing-value, however, can be expressed numerically with a fair degree of accuracy; and it is with this phase of valuation that the present paper is concerned. The utility of a means of comparing numerically the relative smeltiug-values of difierent ores, cokes, and limestones, is self-evident, although it may not have importance in Northern practice, where materials are largely standardized. On the other hand, there are, especially in the South, many furnace-managers who must use a great variety of materials of widely varying grade; and it is with special reference to this district, and in connection with the efficiency-methods which I have elsewhere proposed,' that the methods herein described were devised.

Jan 1, 1913

By M. D. Hassialis, A. F. Taggart

ark' observed some years ago that collector-coating reactions with xanthates and with fatty acids clearly follow paths parallel to those prescribed by the familiar mass-action law for reactions in dilute solutions. He proposed, therefore, the logical hypothesis that they are governed by the solubility-product principle. However, he went astray in the application of his proposal to collector coating by overlooking the fact that coating involves a heterogeneous reaction. A mistaken concept of the meaning of the word adsorption also entered. Wark thought that the concentration of metallic ion that must be used in setting up the solubility-product equation for the coating reaction was that which could be obtained by solution of the mineral. Since this is very low for sulphide ores, and since the amount of the collector ion necessary for coating produces an extremely low concentration, the resulting ion-concentration product, under conditions when coating occurs, is much lower than that which would indicate a saturated solution of the collector-coating compound. Hence he was forced to the position that the solubility product governing the coating is much smaller than the standard solubility product. To justify this position it was necessary to postulate a coating mechanism that did not obey the ordinary laws of chemical reaction. This Wark did by adopting the concept that adsorption is a property of matter, rather than merely a more or less ephemeral local concentration thereof. Thus he says (p. 142 of ref. I): "Adsorption is not a purely physical property of the solid surface, for the specific nature of the adsorbed molecule or ion is important." The result was that he destroyed the great potential utility of his postulate by tying it to this erroneous concept in the words (pp. 142, 143): "It will be obvious that the adsorption solubility product is less than the normal solubility product." The writers have found quantitatively in the case of galena and potassium ethyl xanthate, and semiquantitatively in the case of covellite and the same collector, that the coating reaction does follow the mass-action law to the extent that coating occurs when the ordinary solubility product of the coating compound is exceeded, and that coating does not take place under the reverse conditions. In the course of the investigation leading to the establishment of this fact it was necessary to work with xanthate concentrations so low (down to 0.0004 mg. per liter), that very long conditioning times, and bubble-contact times of as much as 16 hr. were necessary sometimes to follow the reactions. The results have led to some illuminating conclusions as to necessary collector concentrations in normal flotation operations, and the action of the frothing agent in connection therewith' The experimental work comprised accurate determination of the standard solubility product of lead ethyl xanthate, development of a much less laborious

Jan 1, 1947

By M. D. Hassialis, A. F. Taggart

ark' observed some years ago that collector-coating reactions with xanthates and with fatty acids clearly follow paths parallel to those prescribed by the familiar mass-action law for reactions in dilute solutions. He proposed, therefore, the logical hypothesis that they are governed by the solubility-product principle. However, he went astray in the application of his proposal to collector coating by overlooking the fact that coating involves a heterogeneous reaction. A mistaken concept of the meaning of the word adsorption also entered. Wark thought that the concentration of metallic ion that must be used in setting up the solubility-product equation for the coating reaction was that which could be obtained by solution of the mineral. Since this is very low for sulphide ores, and since the amount of the collector ion necessary for coating produces an extremely low concentration, the resulting ion-concentration product, under conditions when coating occurs, is much lower than that which would indicate a saturated solution of the collector-coating compound. Hence he was forced to the position that the solubility product governing the coating is much smaller than the standard solubility product. To justify this position it was necessary to postulate a coating mechanism that did not obey the ordinary laws of chemical reaction. This Wark did by adopting the concept that adsorption is a property of matter, rather than merely a more or less ephemeral local concentration thereof. Thus he says (p. 142 of ref. I): "Adsorption is not a purely physical property of the solid surface, for the specific nature of the adsorbed molecule or ion is important." The result was that he destroyed the great potential utility of his postulate by tying it to this erroneous concept in the words (pp. 142, 143): "It will be obvious that the adsorption solubility product is less than the normal solubility product." The writers have found quantitatively in the case of galena and potassium ethyl xanthate, and semiquantitatively in the case of covellite and the same collector, that the coating reaction does follow the mass-action law to the extent that coating occurs when the ordinary solubility product of the coating compound is exceeded, and that coating does not take place under the reverse conditions. In the course of the investigation leading to the establishment of this fact it was necessary to work with xanthate concentrations so low (down to 0.0004 mg. per liter), that very long conditioning times, and bubble-contact times of as much as 16 hr. were necessary sometimes to follow the reactions. The results have led to some illuminating conclusions as to necessary collector concentrations in normal flotation operations, and the action of the frothing agent in connection therewith' The experimental work comprised accurate determination of the standard solubility product of lead ethyl xanthate, development of a much less laborious

Jan 1, 1947

By Harry A. Lipsitt, Rollins E. Hook, Attwell M. Adair

A necessary condition for a uniaxial stress distribution in compression testing is that the specimen end surfaces make full contact with the apparatus compression plates. In addition all compression surfaces must be machined perpendicularly to the loading axis. In general this condition is not sufficiently fulfilled in a simple apparatus. Therefore on application of the load the compression plate may first touch the specimen at one point only. This may cause crumbling of the specimen if the material under investigation is brittle (e.g., ionic crystals). It also precludes a precise study of the beginning of deformation as the effective cross sectional area is unknown. In addition a complex stress state is set up which renders quantitative work impossible, e.g., on dislocation density and arrangement as a function of stress. To overcome these difficulties a "self-adjusting" upper compression plate is required. A simple and reliable method of achieving this is shown in Fig. 1: A steel hemisphere is placed on the specimen. As soon as the compression plate (which no longer needs precise machining) makes contact with this hemisphere the load is uniformly distributed over the whole specimen surface, and a homogeneous uniaxial state of stress results. An advantage of the method is that the loading is always central, even when the specimen surface is not parallel to the compression plate (Fig. 1, dashed line). Therefore to a first approximation a uniaxial state of stress is maintained if the misorientation of the specimen end surface is small. Two typical stress strain curves of identically prepared sodium chloride crystals are shown in Fig. 2; curve 1 was taken without and curve II with the hemisphere under otherwise identical conditions. The improvement in the accuracy of defining the beginning of elastic and plastic deformation is clearly indicated. The writer wishes to thank the Deutsche Forschungsgemeinschaft for financial support, and Professor P. Haasen for providing facilities for this work.

Jan 1, 1962

By F. Peter

Technical progress takes place in two directions: the improvement of methods, affecting the quality of the product; and increase in the economy of operations, affecting its cost. In the iron-industry, practice is pretty well settled, and revolutionary changes of method are, for the present, not to be expected. Hence, in this industry, the principal endeavor is to reduce costs by the use of labor-saving inventions, such as the machines brought into use during the last decade. But it is not alone necessary to reduce the labor-cost; complete economy requires also a saving in raw material. Under this head we may rank the coal employed as metallurgical fuel; and it follows that progress includes the economic use of fuel, so managed as not to injure quality of product. In the present paper it will be shown how, by suitable utilization of the heat from the furnace, a large portion of it may be made available for other purposes. Such utilization of waste-gases is important in all industries which employ furnaces (especially heating-and smelting-furnaces); and in the first rank of these stand the iron-, glass-, and porcelain-manufactures. The following pages are devoted chiefly to the waste-gases of smelting-works, and especially to those reverberatory-furnace gases which are not combustible.' The object of metallurgical furnaces is either to fuse the material charged or to bring it to a high temperature required for further mechanical manipulation. Leaving out of consideration for the present the reverberatory fusion-furnaces, we have to do with the heating-furnaces employed in connection with rolls, hammers, or hydraulic presses. The temperature to which the material must be

Jan 1, 1914

By F. T. Lee

Directional dependence of strength and deformation properties of the Mount Waldo granite pluton in southeastern Maine is controlled by joints and microfractures whose orientations are linked to flow- induced alignment of microcline crystals. Longitudinal and cross joints which formed during cooling of the mass, as well as much younger sheeting fractures, are commonly associated with subparallel, discontinuous microfractures. The orthogonality of microfractures (open, closed; filled, unfilled; bubble planes) establishes the ease of splitting of the granite. The easiest splitting direction (rift) is subhorizontal, the second easiest direction (grain) is parallel to the cross joints, while the direction of least easy splitting (hardway) is parallel to the longitudinal joints. Static and dynamic measurements made in the field and laboratory established that structural features are responsible for the marked stiffness anisotropy of the granite. In the central part of the pluton the static Young's modulus in the north-south direction averages 31.1 GPa, and 20.9 GPa in the east-west direction; the stiffer direction being parallel to the long C-axes of microcline phenocrysts and microfractures as identified in outcrop, core samples, and thin sections. Vertical downhole sonic measurements of dynamic moduli ranging from 2.5 to 16.2 GPa appeared to be anomalously low when compared to the static horizontal values. However, the field sonic values were confirmed by laboratory sonic pulse testing of oriented cores. The field results reflected closely spaced layers of open horizontal microfractures. Those deformation and strength properties that are closely tied to bubble planes, filled microfractures, and microcline orientation could be extrapolated to greater depths with good hope of success.

Jan 1, 1984

By B. Ramaswami, U. F. Kocks, B. Chalmers

The latent hardening of silver and an Ag-Au alloy was investigated by lateral compression, overshoot in tension and cormpression, and the stability of multiple-slib orientations. The latent hardening of a secondary slip systenz depends on its relation to the primary slip system. For most secondary slip systems the latent hardening is larger for Ag-10 at. pct Au than for pure silver. The maximum increase in. flow stress on a secondary slip system over that of the primary slip system was 40 pct. The work hardening during the lateral-compression test on the latent system after prestress on the primary system is iuterbreted in terms of the preferential distribution of barriers to dislocation movement with respect to the active slip system in work-lzardened fcc crystals. The work-hardening in fcc crystals is mainly due to the dislocation interactions and the barriers to dislocation movement formed as a result of reactions between dislocations of different slip systems. The operation of sources on the latent system depends on the flow stress of those systems; hence, the increase in flow stress of a latent system due to glide on an active system, which is called latent hardening, is an important element in understanding the phenomenon of work hardening. The problem of latent hardening has attracted the attention of many investigators in the past. For example, a theoretical study of the elastic latent hardening of the latent systems due to glide on an operative system has been made by Haasen' and ~troh. These calculations, however, neglect the stress required for the intersection of forest dislocations by the glide dislocations, a factor which would be important for producing macroscopic strains on the secondary slip systems. The importance of this factor will become evident from the results presented here. Attempts have also been made to determine the latent hardening of different slip systems by experimental means by the methods summarized in Table I.3-9 The experimental methods used have been subject to certain limitations. For instance, in the method used by Hauser,9 frictional constraints between the specimen and the compression platen were not eliminated by proper lubrication (see Hos- ford10). Secondly, with the exception of Kocks,6 Hauser,9 and Rohm and Kochendorfer,11 latent-hardening studies have been made on only one of the slip systems, i.e., on either the conjugate or the coplanar slip system; hence, extensive results are not available on the latent hardening of different slip systems in the same materials, with the exception of aluminum.6 It was therefore decided to study the latent hardening of the conjugate, critical and half-related slip systems in silver. Similar experiments were done in Ag-10 at. pct Au to study the effect of solute (gold) on the latent hardening of silver. Lastly, indirect evidence can be obtained by a study of the orientation stability of crystals of multiple-slip orientations in tension and compression. This method has been used by Kocks6 to supplement his studies of latent hardening in aluminum. Similar studies were made at room temperature in single crystals of silver. EXPERIMENTAL PROCEDURE The single crystals of the desired orientations were grown and the tensile test specimens were prepared as described in Ref. 12. The compression tests were made on 1/4-in.-cube specimens. The specimens were cut from single crystals, in the Servomet spark-erosion machine.13 The two cut surfaces were planed using the lowest available planing rate in the machine to minimize the deformation layer. A brass strip was used as the planing tool. This method of preparation ensured plane parallel faces for the compression tests. The deformed material was removed by prolonged etching in a weak etching solution. A weak etching solution was used to prevent pitting of the surfaces and to ensure uniform etching. About 25 to 50 µ of material were removed from all faces by the etching treatment. The specimens were then annealed for 24 hr at 940°C in oxygen-free helium and cooled in the furnace to room temperature over a period of 7 hr. After annealing, the orientation of the specimens was determined by Laue back-reflection technique to make sure that no recrystallization had occurred on annealing. The compression-test technique and setup are described in Ref. 14. The Laue back-reflection technique was used to study the overshoot in tension, the overshoot in compression, and the stability of the axial orientation in tension and compression. The tests were interrupted after every few percent strain to determine the axial orientation. In investigating the overshoot in compression, the operative system was determined by studying the asterism of the Laue spots.

Jan 1, 1965

By D. G. Hartley, P. C. Hayward, K. R. Weller, U. J. Sterns

The major copper loss at Mount Lyell is in the coarsest particles presented to flotation. An analysis of data collected from the five Primary and six secondary ball mill circuits showed that grinding was limited by low breakage rates in secondary mills, possibly due to oversize balk. For five months, the make-up ball size for one secondary mill was reduced from 50 to 30 mm (2 to 1.1 in.). Frequent steady-state tests indicated that overall average breakage rates could be increased by about 70% using smaller balk. A mathematical simulation of the whole circuit with increased breakage rates showed that the resultant finer grind was likely to improve copper recoveries by about 2%.

Jan 1, 1984

By S. E. Hasko

It is the purpose of this note to report the crystal-lographic data for nine new B5A compounds* having the Cu5Ca structure, with A a rare earth and B a transition element, Co, Ni or Cu. In previous papers, some magnetic data1 and preparation and crystallo-graphic data2 for other B5A compounds having the same structure have been reported. Crystallographic data for these compounds are shown in Tables I and 11. These results are in agreement with others of this series reported previously by Wernick and ~eller.' The abnormally large atomic volume of Yb metal3 is not manifested in Ni,Yb, when one compares it with the compounds reported here and the data of reference 2. This is not true for the compound YbAl,, having the cubic Laves structure (MgCuz), to be discussed in other papers.4'5 Thus, it appears that Yb has a valence of 3; i.e., the 2 s and Id electrons are lost to the conduction band.4'5 Lattice constants for four of these compounds prepared by levitation melting have been reported by Nassau, Cherry, and wallace.' The lattice constants

Jan 1, 1961

By Robert C. Emmett, Donald A. Dahlstrom

FOR many years gravitational classification has been employed as a basic tool in beneficiation of minerals and coal. While improvements have been made to increase efficiency and fields of application, the basic flow pattern has remained relatively unchanged in most gravitational classifiers. Feed slurry is introduced into a settling pool wherein the coarser solids settle against either an upward or horizontal fluid current, or a combination of both, and are withdrawn in a concentrated underflow stream. The finer solids below the classification point possess too low a settling velocity and thus are primarily swept out through a weir overflow by the bulk of the fluid. Because of its simplicity, efficiency, and low power and maintenance costs, gravitational classification finds a wide acceptance for separations in the range of 20 to 325 mesh.

Jan 10, 1953

By Henry M. Howe

If a bar of wrought iron or steel is suddenly cooled from a bright red-heat, the contraction which then occurs is considerably greater than the expansion previously caused by heating the bar, so that its final length is considerably less than its initial length. Mr. Thomas Wrightson has investigated this phenomenon,* and has shown that not only does this permanent contraction occur on sudden cooling, but, if the heating and cooling be repeated, say fifty times, a further permanent contraction occurs at each successive cooling. In Mr. Wrightson's opinion, this contraction cannot be explained on mechanical grounds, and he ascribes it to some molecular change caused by sudden cooling; but I think that we need not invoke mysterious molecular changes to explain this phenomenon, which appears to me to be due to very simple and purely mechanical action. Let us consider the cooling as divided into two periods, in the first of which the exterior or skin of the bar becomes almost completely cooled, and hence tends to contract almost to its initial dimensions, while the still hot arid plastic interior contracts but little; in the second period the already cool skin remains nearly constant in temperature, and hence tends to contract but little, while the interior cools from a comparatively high temperature to the ordinary temperature, and hence undergoes great contraction. The excess of the contraction of the skin over that of the interior during the first period tends to make the bar bulge in the middle of its length. This, as well as the decrease of density which occurs, Mr. Wrightson correctly explains. The interior of the bar just sufficed to fill the skin when both were in their initial condition, before being heated at all. At the end of the first period, the volume of the still hot interior is more than the now contracted skin can hold while maintaining its initial shape; and the effect is much the same as when we powerfully blom into a soft India-rubher Lag of the shape of the skin of the bar—it bulges, and tends to approach the spherical shape, in which the ratio of surface to

Jan 1, 1886

By R. Neilson M. E. Clark

(with map on plate I.) THE coal-beds of Canyon City are situated six miles below the town, upon the Arkansas River. At this point the Rocky Mountains have thrown out from their main ridge two spurs. The one to the north, containing Pike's Peak and Cheyenne Mountain, is known as part of the "Rim Range;" the one to the west and south is known as the `1 Green¬horn Range." Against these syenitic mountains, the later rocks are piled and uplifted; at right angles to the direction of this main uplift is the axis of a lesser plication. On the north, west, and south, the pitch is steep, gradually flattening as it approaches the centre of the basin and rising again to the east at a pitch of about 5°, thus forming a perfect basin, the centre of which is only three miles east of the base of the Greenhorn Range.

Jan 1, 1873

By D. J. McAdam, R. W. Mebs

THE technical cohesive strength of a metal means, not the interatomic forces, but the technically estimated resistance to fracture. An example of such resistance to fracture is the so-called "true" breaking stress of a tension-test specimen, the breaking load divided by the sectional area at fracture, According to the prevalent view,8 the technical cohesive strength of a metal, in any particular state as regards prior mechanical treatment and heat-treatment, is determined by a limiting value of the algebraically greatest principal stress.? In two previous papers by one of the authors,14,15 evidence was presented to indicate that the technical cohesive strength of a metal cannot be represented by a single stress value, but that it comprises an infinite number of values corresponding to the infinite number of possible combinations of the principal stresses. The technical cohesive strength thus comprises an infinite number of technical cohesion limits, each representing a specific stress combination at fracture. In the same papers, evidence was presented that plastic extension causes a continuous increase in the technical cohesive strength. Such a variation is not in accordance with the prevalent view that plastic extension first increases, then decreases, the technical cohesive strength.8 In this paper, as in the previous papers,14,15 the algebraically greatest principal stress will be designated S1, the least principal stress will be designated S3, and the intermediate principal stress will be designated S2. The technical cohesion limit under polarsymmetric tension (S1 = S2 = S3) will be termed the "disruptive stress," and the cohesion limit under unidirectional tension (S2 and S3 = o) will be termed the "severing stress." 14,15 The yield strength of a metal, according to the generally accepted theory, may be represented by a constant value of the shearing-strain energy, and hence by a constant value of the sum of the squares of the three principal stress differences. In the second of the previous papers,"' however, evidence was presented that the limiting yield stress decreases with increase in the volume stress, the algebraic average of the three principal stresses.* This influence of the volume stress becomes prominent only in the field of triaxial tension. In the two previous papers, 14,15 diagrams were presented to show the variation of the technical cohesion limit, yield stress, and ultimate stress with the combination of principal stresses and with plastic extension. Those diagrams and the resultant conclusions are derived from experimental data obtained by other investigators. They are based chiefly on results of tension tests

Jan 1, 1943

By C. G. Dunn, F. W. Daniels

IN recent publications1-5 the existence and behavior of subgrain boundaries in high-purity metals has been clearly brought to light. Lacombe and Beaujardl by means of special etching methods disclosed in polycrystalline sheets of aluminum the existence of substructures differing in orientation by small amounts (about 1/4"). Boundaries of these structures at relatively high temperatures had the remarkable property' of moving about while the ordinary boundaries remained stationary. Cahn2 also observed substructures in bent and annealed single crystals of aluminum, zinc, magnesium, and rock salt. The position of subboundaries could be explained in terms of a dislocation mechanism of polygonization in which dislocations move into lines at right angles to the bent glide planes thereby relieving elastic stresses in these planes. Guinier and Tennevin8,6 disclosed the further interesting feature that polygonized structures coarsened significantly upon prolonged annealing. Somewhat similar subgrain phenomena have been observed in silicon iron of commercial purity. Although some evidence for the development of macro-mosaic structures in silicon iron already has been reported by one of the authors6,7 under the phenom-enological term "crystal recovery," much better evidence recently has been obtained due to improved etching techniques. In addition, phenomena regarding structural changes have been uncovered. The present investigation is divided into three parts: (1) The phenomenon of Laue spot sharpening on annealing cold-rolled crystals, (2) the phenomena of polygonization and subgrain coarsening The material used in the present investigation was high-grade commercial silicon iron sheet of nominal composition, 3.3 pct Si, 0.004 C, 0.011 P, 0.010 S, 0.04 Mn, 0.01 Al, 0.04 Cu, 0.01 Sn. Large single crystals of this material Were prepared for cold-rolling or bending as scheduled. Cold-rolling of 12 pct was carried out on a laboratory 8-in, diam rolling mill. The bending deformations were performed by pressing the crystals between a solid Fig. 2—lllustrative foue patterns to show Laue spot sharpening. a (Left)—Specimen as cold rolled, b (right)—After 48 hr at 1400°C. round bar and a mating half cylinder, both heavily greased. Individual specimens were cut from the deformed crystals, and the cut edges were deeply etched prior to annealing. Laue photographs were made using 40-kv tungsten radiation. The technique used to disclose the various subboundaries was an electropolish and electroetch in a bath of chrome-acetic acid.' The anodic polishing done at 22 v was immediately followed by etching at a reduced voltage, which was dependent upon the nature of the subboundaries. Phenomenon of Laue Spot Sharpening on Annealing Cold-Rolled Crystals Fig. 1 gives the initial and final orientations of the specimens cold-rolled 12 pct. Each specimen was annealed at a temperature and for a time which caused significant structural changes as evidenced by alterations in Laue patterns. Representative Laue patterns and micrographs showing the essential changes are given in Figs. 2, 3, and 4. The essential points to be derived from these illustrations follow: 1. Annealing at 950°C clearly develops a substructure with the orientation of the cold-rolled specimen. 2. The subboundaries formed obviously separate regions of nearly the same orientation. Some of the subboundaries appear as a sequence of dots similar to those observed in aluminum by Lacombe and Beaujard,' but whether this is due to extremely small differences in orientation is not known at present. 3. The substructure coarsens upon prolonged annealing. 4. Prolonged annealing also causes a decrease in orientation spread according to Laue spot sharpening'

Jan 1, 1952

By Raymond L. Orr

Calorimetric measurements have been made of the heats of solution of gold axd indium in a number of liquid tin-rich alloys at a temperature of 705°K. Relative partial molar enthalpies of gold were determined as a function of dilute solute concentrations in the binary Au-Sn system and in the ternary Ag-Au-Sn and Au-In-Sn systems. Relative partial molar enthalpies of indium were determined for dilute solute concentrations in the In-Sn, Ag-In-Sn, and Au-In-Sn systems. Through application of the interaction coefficient concept introduced by Wagner and more recently extended by Lupis and Elliott, ualues have been obtained for the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. The results are inte@reted in terms of solute atom distributions through comparisons with the predictions of dilute solution models. INTEREST in the thermodynamic behavior of dilute liquid alloys stems from two primary sources. From a practical viewpoint, it is often of importance to know or to be able to predict the effect that one solute will have on the thermodynamic properties of the other solutes in a multicomponent system. Studies of dilute solutions may also be rewarding from the theoretical point of view. Some of the difficulties arising from the more complex interactions possible in concentrated solutions are avoided, leading to easier interpretations in terms of solutibn models and bonding energies. For example, in a binary alloy the limiting values of the partial molar properties of the solute represent the case for which each solute atom is completely surrounded by atoms of the solvent, and no other interactions are possible. Solute - solute interactions in dilute solutions are conveniently treated by the interaction coefficient concept of ~agner.' Using a Taylor series expansion for the logarithm of the activity coefficient, In yi, of a component, i, in a solution consisting of dilute solutes with atomic fractions xi, xj, xk, and so forth, in a solvent, s, and neglecting the second- and higher-order terms, Wagner obtained the expression: Where Wheyz is the limiting value of yi in the pure solvent, s. The interaction coefficients, e:, e:, and so forth, are defined by: Since yi is related to the excess partial molar Gibbs energy of component i by GfS = RT In yi, E: is re- ferred to as the "Gibbs energy interaction coefficient". Lupis and Elliott~ extended Wagner's treatment to the relative partial molar enthalpy, aHi, and the excess partial molar entropy, qS. They defined the enthalpy interaction coefficient as: and the excess entropy interaction coefficient as: leading to expressions similar to Eq. [I]: The three interaction coefficients are related by? The self-interaction coefficients, E:,qf,and at, represent the effects of interactions between atoms of component i in solvent s; €3, q{, and 03 represent the effects of interactions between i and j atoms in solvent s; and so forth. From the Maxwell-type relationships between partial molar quantities, it may be shown1'2 that e{ = ej, r}\ =tj), and ai - crj. Experimental determination of the interaction coefficients requires extremely precise measurements of the appropriate properties as functions of solute concentrations in very dilute regions. Few such data exist for intermetallic alloys, even for binary systems, because of experimental difficulties. This is especially true with respect to enthalpy data for dilute alloys. Examination of the compilation of data for binary alloys by Hultgren, Orr, Anderson, and ~elle~~ reveals that determination of limiting values of &fii(Xi =0) often requires extrapolations to infinite dilution from xi = 0.05 to 0.10. Direct measurements of the enthalpy interaction coefficient, qi, for multicomponent systems are virtually nonexistent. This quantity is of course subject to direct calorimetric measurement, but its determination must be limited to cases where high experimental precision is possible. The heats of solution of gold and indium in liquid tin can be measured with relatively high precision, which makes determinations of 73 involving these metals as the measured solutes experimentally attractive. This paper presents the results of such determinations of the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. MODELS FOR DILUTE-SOLUTION BEHAVIOR Random-Solution Behavior. In the quasi-chemical treatment of solutions, only nearest-neighbor bonds are considered, and a composition independent value

Jan 1, 1967

By A. G. McGregor

IN THE Southwest a number of large steel chimneys discharge the gases from the copper smelting furnaces. Some of these chimneys show no deterioration after twenty years, others show serious deterioration after tour years service. A steel stack 20 ft. 7 ½ in. (6.3 m.) in diameter by 279 ft. (85 m.) high, Fig. 1, used for roaster gases only at the Calumet & Arizona Mining Co.'s plant at Douglas, Ariz., was lined to the top of the bell, 40 ft. (12 m.) from the base, with common brick placed on end, lime and cement mortar being used. Above the bell, the stack was lined with 4 by 4 by 8 in. (10 by 10 by 20 cm.) building tile, placed on end, making a lining 4 in. thick. The tiles were supported on angle-iron rings, riveted to the inside of the chimney shell about 15 ft. apart. The chimney was put into use in the latter part of 1913. Four years later, considerable of the tile lining had fallen out of place and mixed with the flue dust at the bottom of the chimney. About a year later, several . flattened and distorted sheets were noticed about 70 ft. below the top. An investigation showed that the thickness of these distorted sheets, which was originally ¼ in., had been reduced one half. One year later, or six years after the chimney went into use, several holes, a square foot and smaller in area, appeared near the flat spots mentioned. Soon afterwards, when the chimney was shut down for repairs, it was found that most of the tile lining for 125 ft. from the top had fallen out and that the steel shell was badly corroded; but where the lining remained in place the shell was undamaged. Many of the tile which had fallen out of place had become soft or flaky and crumbling, others were as hard as when placed. An analysis of the hard and soft tile is shown on p. 2. These tile were of a fireclay mixture, and were used instead of common brick on account of lower cost. The steel forming the upper 125 ft. (38 m.) was replaced, and a 4 ¼ -in. (11-cm.) lining of firebrick was laid from the bell to the top of the chimney. The brick were placed on end, wedges and keys being used. After each 8-in. course was set, keyed, and wedged tight, thin mortar -water, sodium silicate, and finely ground silica-was worked into the joints. The brick are supported on angle-iron rings, every 15 ft., in the same way as the tile.

Jan 1, 1921

By J. W. Sandelin, L. S. Birks

The group five metals, vanadium, niobium, and tantalum all show cold-rolled textures of {100)(011) and {112)(0ll) with a preference for the (100) in vanadium and niobium and for the {112) in tantalum. Recrys-tallization texture of (100) and (111) was reported1 for vanadium after annealing (no temperature stated). For tantal~m ,~ annealing below 1200°C strengthened the (112) texture but the (111) texture increased and was predominant as the annealing temperature was raised to 2500°C. Annealing niobium up to 1100°C strengthened the ( 100) texture and developed a weak (111) texture.' In the present work niobium has been annealed up to 2000°C. Nearly 70 pct of the grains showed {111) texture with only a weak (112) component and an insignificant (100) component remaining. In addition, double-crystal rocking curves were used to follow the increase in crystal perfection of the grains with increased annealing time. Material and Treatment. Samples i by 4 in. were sawed from & -in.-thick cold-rolled niobium sheet obtained from Wah Chang. Chemical analysis of the material showed it to be 99.4 pct pure with tantalum as the major impurity. Individual pieces were annealed for 2, 15, 30, and 60 rnin in a vacuum of 10'* Torr using an rf generator. They were etched until the grain boundaries were well-defined, Fig. 1. Average grain size varied from 1 mm for 2 min annealing to 2 mm for 60 rnin annealing. Experimental Results. Preferred Orientation. The orientations of 97 of the 117 grains in the specimens of Fig. 1 were determined by back-reflect ion Laue patterns. A General Electric 10-cm-diam cylindrical camera was used rather than the conventional flat camera in order to record more of the low-index spots. The method proposed by Forest, Barton, and schieltz4 was used to transform the cylindrical film patterns to standard stereographic projections. Table I gives the compilation of data. Even 2 rnin anneal at 2000°C is sufficient to yield a strong (111) preferred orientation, and the percentage of grains with this orientation increases steadily with annealing time at the expense of all other orientations. Crystal Perfection. X-ray topographs were taken of each specimen in both the (111) and (112) orientation using the method described by Birks and Grant.' As the anneal time increases, the grains become larger and the individual reflections become slightly more uniform in intensity, indicating an increase in crystal perfection. For a more quantitative measure of crystal perfection, it was necessary to measure the double-crystal rocking curve. The spectrometer employed was a Gaertner instrument of Compton design. LiF was chosen for the first crystal because the (400) reflection with d spacing of 1.05 AU is a good match to the (222) niobium reflection with d spacing of 0.95 AU. CuKp radiation was used in order to further reduce the d spacing mixmatch correction.' A variable aperture was placed between the LiF and the niobium specimen so that a single grain or even a small portion of a grain could be examined. Fig. 2 shows typical rocking curves for the four annealing times. For the 2-min specimen, a single peak is observed with 10' of arc full-breadth at half maximum. As the annealing time is increased to 15 or 30 min, several sharper peaks of 40 to 80" breadth can be seen within a single grain. After 60 rnin anneal only a single peak of about 30" is observed. Table I1 shows the corrected rocking curve breadths and the dislocation densities, ND. The latter were calculated from the equation7 where W is the corrected rocking curve breadth at half maximum in radians and b is the effective Burger's vector. For (110)(111) slip in niobium, b is 2.86 AU. Discussion. The annealing of cold-rolled niobium at 2000°C causes rapid preferential growth of grains with {ill} orientation. After only 2 rnin annealing time, 35 pct of the grains have the (111) orientation, and after

Jan 1, 1968

By B. H. Kear, H. G. F. Wilsdorf

After a few percent strain, dislocations in disordered Cu3Au are arranged in groups in ulell-defined slip planes, which contrasts with the more or less random distribution of dislocations in the corresponding ordered alloy. Unusually long and straigkt dislocation segments observed in the ordered alloy are interpreted in terms of cross slip of screw dislocations from their slip planes into cube planes. It is proposed that cross slip, and also dislocation reactions of the Lomer type, play an important role in work hardening of the ordered alloy. ACCORDING to to dislocations in the disordered lattice are only partial dislocations in the corresponding super lattice, so that in the super-lattice dislocations must occur as pairs, with each pair connected by a ribbon of antiphase boundary. Recently, striking confirmation of the theory was obtained by Marcinkowski, Brown, and Fisher3j4 in a study of dislocation configurations in thin foils of the Cu3Au alloy by transmission electron microscopy. In the present investigation, the observations made by these workers have largely been confirmed. Moreover, it has been found that dislocations in the plastically deformed ordered alloys are often unusually long and straight. This paper is mainly concerned with these new observations. A tentative explanation is offered in terms of cross slip of dislocations in the ordered alloys. PREPARATION OF SPECIMENS An alloy close to the stoichiometric composition Cu3Au was prepared by melting together high-purity copper and gold (99.995 pct) under vacuum in a graphite mold. The resulting ingot was rolled down and cut into strips 1 1/2 by 1/8 by 0.005 in. in thickness. All strips were annealed at 900°C for 3 hr and cooled to 500'~. A few of the strips were quenched from ~OO'C, while the remainder were slowly cooled in the temperature range 400" to 150°C at intervals of a few degrees every 24 hr to produce a high degree of order. After this annealing treatment the average grain size of the material was about 0.1 mm. Material in different states of order was obtained by reannealing fully ordered material at temperatures below the critical temperature: followed by quenching. The equilibrium degree of order attained at a particular reannealing temperature was obtained from the paper by Keating and warren.' A simple hand-operated tensile jig was used to give the strips the required amounts of plastic strain. Following straining, a number of specimens were cut from each strip by means of an electrolytic cutting device.= Finally, each specimen was thinned electrolytically using the polishing procedure described by Bakish and Robertson,7 and these thin sections were examined in the Philips EM-100B electron microscope operating at 100 kv. EXPERIMENTAL OBSERVATIONS Antiphase boundaries. The average domain size in the ordered alloys was found by direct observation to be about 0.25 p. Also, it was observed that the grown-in configuration of antiphase boundaries was changed little by plastic deformation, at least up to 6 pct strain. Fig. 1 shows an electron micrograph of a thin foil of partially ordered alloy (S - 0.8) after 3 pct strain. The micrograph shows a few dislocation pairs and a somewhat crystallo-graphic network of antiphase boundaries. The normal to this foil was found by diffraction analysis to be approximately 11121, with principal directions in

Jan 1, 1962