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By M. R. Geer, H. F. Yancey

0. R. LYONS*—I know that we are all interested in hearing about problems that other people have. To most of the people from the eastern part of the United States, this kind of coal preparation is completely different. It represents washing difficulties that most operators have never experienced, or, if they have, they have refused to consider them because there are coals that are much easier to wash and, therefore. they leave the more difficult ones alone for the time being. E. R. McMILLAN†—I think the au-thors have summarized the material very well. Dr. Yancey has spent a great many years in the study of washing coals, as has Mr. Geer. I might comment briefly on some of the plants that were mentioned, plants with which I have had some con-nection, particularly those of our own company, the Northwestern Improve-ment Co. I would like to point out this: that ill each case, a great deal of work was done in the way of preliminary studies of washability of the coal before plants were built. The first plant of any size built in Roslyn field was mentioned in the paper. This central cleaning plant was designed and built to handle coal from three different mines. I might say that prior to 1935, the year in which the plant was built, the coal was used largely as railway fuel, close to a million tons annually. But as mining increased in depth, it became increasingly difficult to separate and gob much of the impurities underground, with the result that the run-of-mine coal became so high in ash that the railroad eventually was forced to consider installing some kind of preparation plant at the mine. We spent about a year in preliminary studies in cooperation with the Bureau of Mines to find out the best type of plant that would clean the coal. The result, as Mr. Geer has explained to you, is a rather complicated plant, but it is doing a very satisfactory job. We have, however, made a number of changes and improve-n~euts since it was first built. The last addition was the, installation of a cen- trifugal drier to dewater the minus ¼ in. size. We are now contemplating installing heat driers for further drying of minus ¼ in. We use Vissac heat driers for drying the stoker coal, the ¾ to in. The demand for drier coal, for both railway and industrial use, is forcing us to further drying of the coal. The plant that was mentioned as having been built in Pierce County, during the war, was a government sponsored plant. I happen to have had some connection with its design, construction and initial operation. We did what we thought then, and still think, was a very thorough job of preliminary studies in cooperation with the Burea of Mines of the coal from that field. The plant was as good a plant as could be built with the equipment available at that time, 1943. The plant that was mentioned as having been built at Ravensdale for treating the McKay coal was rebuilt about two years ago, and in addition to the modified Elmore jig washer that was mentioned. we added a coucentrating table for re-cleaning the minus 3/32 in. Our object there was to produce a commercial

Jan 1, 1950

By W. B. Hickman, J. J. Pickell, B. F. Swanson

Many physical properties of the porous media-immiscible liquid system are dependent upon the distribution of fluids within the pores; this in turn, is primarily a function of pore structure, liquid-liquiri interfacial tcnsion and liquid-solid wetting conditions. The cnpillary pressure hysteresis process provides a means of investigating the influence of pore structure upon fluid distribution for consistent sur/acc conditions. Invcstigntiot2s indicate that residual non-wetting-phase saturations /ollozuir,g the imbibition process (i.e.,wetting phase displacing nor2-wctting phase) are dependent upon both pore structure and initial non-raetting phase saturation and suggest that residual fluid is distributed as Discontinuous ,globules, one to a few pore sizes in dimension, thrnugh the entire range 01 pore sizes originally occupied. It clppears that air-mercury capillary pressure dala adequntely rellect the distribution of fluiris in a water-oil system when strong wetting condition preliczil. An oil-air counter-current imbibition technique has also been found to provide a rapid rneans of obtaining residual-initial saturation data. In a majority of cnses, rcsidual saturations detf-rniinecl from the oil-air or air-mercury process reasonably approximate residual oil saturation following water drive of a strongly water-wet medium. INTRODUCTION A reliable estimate of recoverable reserves depends not only on the amount of original oil-in-place but also on pore geometry and distribution of fluids within the pores. A critical parameter determining the recovery from a reservoir under waterflood, for example, is the amount and distribution of residual oil within the various rock types present. The purpose of this paper is to investigate the mechanism of capillary trapping and assess its importance in laboratory measureqents of residual oil saturation. The degree of wettability of a reservoir rock is recognized as an important factor in waterflood or imbibition experiments. In this paper, however, only the water-wet case has been considered. Considerable experimental evidence1 suggests that for water-wet rocks, capillary forces predominate in tile distribution of fluids and that viscous forces in the range normallv of interest in the reservoir have a minimum influence on residual oil saturation. It follows that if the ultimate recovery is controlled by pore geometry, a unique residual non-wetting phase saturation should exist for a given set of initial conditions. Two laboratory procedures.found to be extremely useful in the study of pore structure and degree of fluid interconnection at various saturations are decribed. Although air-nercury capillary injection curves have been used2 previously to characterize the drainage case, the withdrawal or imbibition case can provide valuable supplementary data. The air-mercury process, however, has several disadvantages; it is difficult to run in a sufficiently accurate manner, mercury does not always act as a strongly non-wetting liquid and in the air-mercury process the sample is rendered unsuitable for future analyses. An alternative process is described in which air is the non-wetting phase and naptha, hentane, octane or toluene is the wetting phase. INTERFACIAL TENSION AND CAPILLARY PRESSURE Interfacial tension between immiscible fluids is due to the difference in attraction of like molecules as compared with their attraction to molecules of the neighbouring fluid. This net attraction results in a tension at the interface. To extend the interface; thus, interfacial tension s can also be thought of as free surface energy. Interfacial tension is normally expressed as dynes/cm, and interfacial energy is measured in ergs/cm2 hence, both have dimensions ml A 2 and are numerically equal.

Jan 1, 1967

By A. M. Gaudin

IT is only in recent years that substantial progress has been made in developing a physico-chemical picture of the solid state. The molecular concept, so useful in dealing with gases, was naturally carried over to the field of crystalline solids; it has resulted in the firm implanting of erroneous concepts that only now are being eradicated successfully. Two simply written and effective books on the subject are Crystal Chemistry by Stillwell1 and An Introduction to Crystal Chemistry by Evans.' A more complete treatment of the subject is available in a book by Wells.' The monograph by Hückel4 also touches on a subject most easily perceived by reference to the brief introduction by Bragg,5 that master of the field. These texts make it clear that while some solids are built of molecules, many are built of ions, others of atoms connected in the form of giant molecules, and still others of cations and electrons. The various lattices in which these entities are systematically arranged, the joint use of several of these entities, and the transitional character of some of the bonds make for the great variety of crystalline solids. The purpose of this paper is to point out a most important corollary of present views on the structure of solids. In this connection the classification of solids in Table I is helpful. Atomic crystals are those formed by the noble gases, e.g., helium and argon. They are soft, sublime at very low temperature, of very low specific gravities, and not encountered in ores. Molecular crystals are uncommon among inorganic materials, common among organic materials. Typical examples from both inorganic and organic fields are sulphur, iodine, naphthalene, benzene, and carbon tetrachloride. These crystals are soft and have low specific gravities; where the molecules are small, the sublimation temperature is low. Filament and sheet crystals are rare. They are typified by elemental selenium and elemental arsenic, respectively. Graphite and molybdenite come near being sheet crystals. These crystals are soft in some directions, tough in others, sublime at various temperatures. Diamantine crystals, typified by diamond, are very few in number, stable at high temperatures, and extremely hard. Ionic crystals are common. Most salts, acids, and alkalies belong in the two classes of ionic crystals; examples are rock salt, fluorite, calcite, and angle-site. The salts, acids, and alkalies that do not belong in these classes are more properly regarded as transitional between ionic crystals, framework crystals, and diamantine crystals, e.g., ice and quartz. Fiber crystals are relatively uncommon mineral-ogically speaking, but common in the fields of living processes. Examples are asbestos, silk, cellulose, and wool. Many fiber crystals are so little known even now that their crystallinity may be doubted. Layer crystals, among the more interesting and useful of solids, include a wide variety of substances

Jan 1, 1956

By R. A. Pallanch

Probably one of the most perplexing problems with which a mill operator contends is the proper evaluation of his mill results. True, he accurately determines his recoveries of metals and grades of products monthly, weekly, and often daily. These figures do not of themselves directly translate to mill economics. When one figure is unusually good there may be an offsetting circumstance. The advantage of high lead or zinc concentrate grade may be offset by poorer recovery; high lead recovery may be offset by poorer zinc recovery, or vice versa; and so on. Besides, grades or recoveries may not of themselves mean more than a reflection of the grade and character of the ore during the period under study. What the operator sorely needs is some one measuring stick that tells him when he has achieved his greatest return, regardless of grades or recoveries—for if he knows his methods and practices are yielding the optimum return he need no longer concern himself with the assays of products and tailings, or the corresponding distribution of metal values. At first blush it would appear that the obvious answer to this is the actual money return to the mill. Paradoxical as it may seem, however, money return does not make a dependable yardstick any more than do grades and recoveries, as ore condi- tions would vary enough to bring about greater money return during periods when the actual metallurgical work is not as good. The mill operator, of course, should always aim for the greatest return on the ore, once it is in the mill bins, with proper attention always to mill treatment cost. The need of a proper yardstick becomes more imperative with the increasing complexity of the problem. In the case of a simple, single-product operation on a fairly uniform ore, in which only one metal is of significant importance, the need is not great, as grade and recovery pretty well tell their own story. At the other extreme is the operation that makes three or four separate marketable products from a complex mixture of heterogeneous ores that vary tremendously in individual metal contents and ratios, degree of oxidation, and other characteristics, and in which gold, silver, copper, lead and zinc are all significant values. Economic Recovery The first attempt at obtaining a proper single yardstick for a fairly complex ore with which I am familiar is the use of the ''Economic Recovery" term at the lead-zinc flotation mill of the Sunnyside Mining and Milling Co., Eureka, Colorado. This method had been applied there early in Sunnyside flotation-mill history (not later than 1920) and credit for the innovation I believe belongs to Messrs. Kuryla and Marquand. The term "Economic Re-

Jan 1, 1949

By P. A. Beck, S. Kohara, M. N. Parthasarathi

IT has been shown1,3 that many observed phenomena related to annealing textures in f.c.c. metals can be adequately accounted for, at least in a qualitative way, by considering the orientation dependence of the boundary mobility, without any hypotheses concerning preferred orientation of nuclei. It was noted1 that this approach is particularly successful in the common cases of primary recrystallization in highly cold-worked polycrys-talline metals, where nuclei occur in great abundance, and that in the other extreme case, where the number of nuclei is very limited, or even only a single crystal is grown, the orientation dependence of boundary mobility has only a small effect, or none at all, on the orientations resulting from annealing. Recently Dunn described examples3-6 where observed secondary recrystallization textures apparently cannot be accounted for on the basis of oriented growth alone, but also require oriented nuclei, or at least the absence of nuclei in certain orientation ranges. In general, the great difficulty in correlating the preferred orientation of recrystallized grains with that of nuclei is inherent in the fact that nuclei are by nature very small, and that they are usually identifiable as "nuclei" only after growth, i.e., after they have already been subject to growth selectivity. An investigation was carried out by Liebmann and Lücke,' and also a very similar one by Graham and Cahn,' to obtain quantitative information on the orientation depend- ence of boundary migration rates in the recrystallization of slightly deformed aluminum single-crystal rods or plates, in which artificially nucleated recrystallized grains of predetermined orientation were grown. Liebmann and Lücke foupd maximum boundary mobility for boundaries across which the misorientation corresponded to a rotation of 40 deg around a common [Ill] axis, in accordance with earlier conclusions.9,1 Also, they confirmed that such an orientation relationship predominates among crystals growing into slightly extended single crystals from presumably random artificial nuclei. On the other hand, Graham and Cahn found no preferred orientation among crystals grown in a similar manner. It is not as yet known how these observations may be reconciled with each other. The view has been expressed in various papers5'10,21 that selective growth based on the orientation dependence of boundary mobility is not in itself sufficient to account for the formation of sharp re-crystallization textures, such as those often observed in highly deformed polycrystalline metals after annealing. The present work was undertaken to ascertain whether or not it is possible to obtain a sharp re-crystallization texture in a case where random nuclei are assuredly present in large numbers. It was previously found1' that high-purity aluminum crystals rolled 80 pct on the (110) plane in the [1T2] direction, when suitable precautions are taken, may be annealed for periods of about 1000 sec at 350°C without recrystallization. It was also found that the reluctance to recrystallize in this case is due to the scarcity of material in sufficiently deviating orientations to serve as nuclei. By using such a matrix,

Jan 1, 1959

By G. W. Thomas

A simplified mathematical model of underground conduction heating in a system of limited permeability is presented. The model applies to underground retorting of oil shale, or to reservoirs containing extremely heavy oils. We assume that heat is introduced at a constant rate into a horizontal fracture which communicates between wells. The radial temperature distribution along the fractured surface is approximated by a step-function. Heat transfer away from the fracture is assumed to be by vertical conduction, and all convection effects are neglected. The model also takes into account the possible temperature dependence of thermal conductivity. A general expression for calculating the growth of the step-function temperature distribution with time is derived. The use of this expression and solutions to the one-dimensional heat equation make it possible to construct isotherms. Expressions for calculating .oil recovery, well spacing and heat efficiency are also given. An example calculation is presented for the conduction heating process in oil shale. Finally, the effect of the heat transfer coefficient between the gas and the fracture boundaries is investigated. INTRODUCTION Thermal recovery processes of oil recovery fall into the four general areas of hot fluid injection, forward combustion, reverse combustion and conduction heating. The first three of* these processes have been rather extensively studied in the past decade from both the experimental and theoretical points of view. As a result, it is possible to make reasonable engineering predictions and analyses of these processes. Little attention has been devoted, however, to the conduction heating process other than to note its possible utility.I To a certain extent, conduction heating cannot be divorced from the other regimes cited above, insofar as these provide the source of heat energy. In the conduction heating process, heat is introduced (either by combustion in the forward or reverse mode or by hot fluid injection) into a small fraction of the total reservoir thickness. This fraction may be either a streak of high permeability or an interwell fracture. Heat penetrates by conduction into the adjacent, less permeable regions of the oil-bearing rock, where the direction of conduction is essentially perpendicular to the streak or fracture. The heated product then drains by gravity or is gas driven to production wells. Conduction heating is probably most applicable to systems containing immobile bitumens such as tar sands and oil shale deposits and perhaps to low-permeability reservoirs containing highly viscous crudes. The mechanism also acts in combination with other thermal processes where fingering or overriding of a bed occurs. It seems probable that in at least one field test, conduction heating of this type was very influential.2 In this presentation we give a first approximation to some of the quantitative aspects of conduction heating. Marx and Langenheim3 treated a similar problem where they focused attention upon the injection interval, which spanned the total reservoir thickness. In their model, conduction heat losses to the bounding media imposed a practical limit on the calculated heated area. In the present study, however, we shall confine the injection interval to a small fraction of the reservoir thickness and assume it has no heat capacity. We therefore direct our attention to regions outside the injection interval into which the conduction of heat is beneficial. In particular, we will endeavor to locate specific isotherms in the media bounding the injection interval. Furthermore, we will construct our model to allow the thermal conductivity to vary arbitrarily with temperature. Thus the model will be applicable to underground retorting of shale where variations in thermal conductivity may be important. THEORY We consider the rock matrix to have no or, at best, a very limited permeability; consequently a

Jan 1, 1965

By L. E. Murr, P. J. Smith

A study has been made by transmission electron microscopy of thin foils of 304 stainless steel fatigued external to the electron microscope in reversed bending, and of thin foils fatigued directly within the microscope in alternating tension. The build-up of stacking faults in the thin foils during fatigue zoas correlated with the dislocatirm structures found in thin films prepared fror fatigued bulk specimens. The performance of the special devices designed for fatigue of thin foils so outlined and the importance of alternative methods of preparation of more uniform fatigue specimens bY vapor deposition are emphasized. INVESTIGATIONS on fatigued bulk aluminum1,' and stainless stee13j4 have revealed the existence of dislocation substructure on examination by transmission electron microscopy of electrolytically thinned foils representative of these bulk specimens. While this technique has proved extremely valuable, it has several shortcomings. First, the method of fatiguing bulk specimens and then thinning to foil for electron-transmission observation allows only one observation of internal structure at any one portion of the fatigue life. Second, thinning the bulk fatigued specimens to foil results in the loss of at least one original surface. Thus, what one sees in the remaining electron-transparent sections is an internal dislocation or fault structure which in many cases cannot be correlated with the original surface markings. This is an undesirable feature, since it is well-known that metal surfaces play an important part in the fatigue process.5 An obvious third undesirable feature of the thinning-from-bulk technique is the fact that static observations have difficulty (in the case of fatigue) explaining the mechanism of a dynamic process. What is required then is a method whereby a selected thin area can be continuously observed either while undergoing cyclic deformation or at various fixed stages of fatigue deformation. While Murr and wilkov6 have reported some success with an apparatus designed to fatigue thin metal foils directly within the electron microscope, the nature of the specimen-mounting procedure and the mechanical features involved in the adaptation of the fatigue device to the electron microscope make this method difficult to operate. It was not possible, for example, to make frequent observations of a selected area because of difficulty in maintaining a chosen area in a stable viewing position inside the electron microscope. Except for the build-up of a dislocation substructure and what are commonly referred to as "slip striations", little else has been reported from observations on thin-foil sections prepared from bulk fatigue specimens. segal17 has found "slip striations" in stainless-steel fatigued specimens which were electropolished from both sides, but gave no explanation as to their origin or identity in terms of lattice imperfections. The research to be reported in this paper was undertaken with the following objectives in mind. First, an attempt was made to devise a technique or techniques whereby thin metal foils could be fatigued and repeatedly observed by transmission electron microscopy. Second, it was hoped that some correlation could be made between deformation striations found in fatigued thin transmission specimens and thin foils prepared from bulk fatigued specimens. These investigations illustrate quite convincingly that a feasible method is available for the direct study of the fatigue mechanism and similar dynamic phenomena in thin transmission specimens inside the electron microscope. I) EXPERIMENTAL METHODS Three modes of specimen fatigue and observation of fatigue damage were used. These involved fatigue of thin-foil specimens in a special arrangement external to the electron microscope and observation of a selected area at various stages in the fatigue life, the fatigue of thin-foil transmission specimens inside the electron microscope, and the fatigue of bulk specimens external to the electron microscope followed by thin-foil preparation for direct observation at predetermined stages. Design of the External Fatigue Clip and Specimen Holder for the Hitachi H.U.11 Electron Micro-scope. The purpose of the fatigue clip was to provide a reversed bending fatigue stress to a thin-foil transmission specimen outside the electron microscope. In order to accomplish this, a flat-bottomed, U-shaped brass clip was made as shown

Jan 1, 1965

By H. R. Banks

PONDERING the action of a ball mill employed to carry on comminution from the product of fine crushing to the point where flotation, cyanidation or other concentrating methods are applicable, one wonders where this machine had its origin. When Henry Wadsworth Longfellow reiterated the observation of that older poet Von Logau, and wrote “Tho’ the mills of God grind slowly, yet they grind exceeding small," he probably visualized the type of mill that was employed in medieval times for the production of flour, and can therefore not be considered as having gained admittance to the fraternity of millmen, on behalf of, either poet. He does, however, make it quite clear that the efficiency of even these Mills of Destiny was low, and to that extent voices a characteristic of fine-grinding equipment that has been the bugbear of all metallurgical engineers. PRINCIPLE OF BALL MILL The principle of the ball mill probably is traceable to the action along the coast line of oceans or lakes, or in the mountain streams. Wave action on rocks and pebbles, close to the shore line, gives the potential energy to the grinding media, which, in their rolling and tossing, break down the sands, and the resultant "pulp" carried out from the shore is classified and settles out in sizes ranging downward to extremely fine mesh. Surely, these are the real mills of God. If we allow our minds to dwell on the total tonnage that has been handled in this way, adding to the sands and clays at present in existence those enormous tonnages of metamorphosed sedimentaries, we sense the vast quantity of rock that has been so reduced. Is it not likely, therefore, that the answer to the beginnings of pebble milling, and eventually ball milling, came through the perception of this natural mill by one of our engineering forebears? METHODS OF GRINDING The relatively low return of mechanical input to a ball mill, in terms of useful work accomplished, has always intrigued me immensely. The potential energy absorbed by a ball raised to a high point in its path is apparently released with a very small return in useful work. Is the ball mill the most desirable means of fine grinding, or is there some other method through which we can recover a reasonable amount of the energy input in terms of useful work? Some years ago, on his retirement, H. W. Hardinge was questioned as to his thoughts on the trend of fine-grinding equipment. As I recall, his prophecy at that time was that the most likely field for improvement in grinding media would be toward a charge of flat disks with some mechanical scheme to cause them to slide over each other. Undoubtedly, Mr. Hardinge went through the usual experience of the muller and bucking board, the customary introduction of the budding millman to his calling. I have often wondered, but have never got beyond the wondering stage, as to the

Jan 1, 1945

By Paul Beck

WHILE the recrystallization properties of most of the practically important metals are known in considerable detail, those of lead are still relatively little known in spite of some valuable contributions in recent years. This condition probably is due to the difficulties involved in applying the usual methods of investigation. The microscopic method of discriminating between the elongated deformed grains of the familiar lenticular shape and the equiaxed recrys-tallized grains is not successful with fully refined lead: lenticular grains cannot be seen under the microscope with any amount of deformation whatever. The probable cause of this phenomenon was recognized long ago. With large deformation the time of recrystallization at room tem-perature is shorter than the period of preparation of the specimen for microscopic examination; with small deformation the deformed grains are not noticeably elongated in the first place. However, with small deformation the migration of the grain boundaries can be observed. The only systematic investigations yet published on the recrystallization of lead, those by R. S. Russell,1-3 make use of the conditions just described. Russell considered recrystallization completed when no further migration of boundaries could be observed. A serious objection to this method arises from the fact that there is no evidence to support the view that grain-boundary migration results only from recrystallization. If such migration does result from other sources after recrystallization is com-pleted-after the deformed grains have been replaced by new unde-formed grains-the "time of recrystallization" as determined by Russell may be too long. Furthermore, the method is subject to the above-mentioned limitation because of the unavoidable period of preparation of the sample. According to Russell, even with the fastest technique 5 min. elapsed before the deformed samples were ready for examination, and consequently no recrystallization time shorter than 5 min. could be measured.

Jan 1, 1939

By AIME AIME

THE papers presented at the geophysics session" on Feb. 17 were concerned largely with three aspects of the science. The first ones dealt with the transmission of elastic waves through the earth, then electrical methods came in for their share of attention and finally, the question of the teaching of geo- physics came up for the first time at these meetings. Also, for the first time, there was a symposium of mining men on the practical value of the new science. The paper (T. P. 267) entitled "Seismic Propagation Paths" was presented by Donald C. Barton in the absence of the authors. It dealt with an investigation of the speed of propagation of seismic waves. The latter travel in a straight line when proceeding at a constant velocity, but if the velocity increases at increasing depths, the line of travel becomes a curve. Under the assumption of the authors this curve is found to be the arc of a circle, and their paper gives calculations for reflected and refracted wave paths under these circumstances.

Jan 1, 1930

By G. A. Moore

A brief review is given of methods designed to produce metallic iron of high purity, and typical results are listed. A recent method, utilized at the National Bureau of Standards, consists of the extraction of ferric chloride by ether, reduction of this ferric chloride to ferrous chloride, further purification of this chloride, and the subsequent electrolytic deposition of metallic iron. iron produced by this procedure apparently is softer than, and otherwise different in properties from, any iron previously prepared and contains appreciably smaller amounts of impurities. THE history of attempts to produce "pure" iron reaches to antiquity and it may be presumed that each ancient armorer who succeeded in making a better steel concluded, correctly, that he had done a better job of removing the "base metals," and incorrectly, that he now at last had a "pure" metal. Early metallurgical papers mentioned use of "pure iron" in making alloys—this "pure" iron in most cases being inferior to some commercial stocks of the present time. Improvement has been continuous, and usually at a sufficient rate to convince each succeeding group of workers that they, at last, were using the really pure metal (until the analysts also improved their techniques to again discover the impurities). These adventures were reviewed in some detail by Cleaves and Thompson.' Although the ores of a metal may be abundant, difficulties in extracting it may make the pure metal very rare. When impurities are restricted to a total of a few parts per million, nearly all pure metals become rarities. Lead, copper, gold, mercury, silver, zinc, aluminum, bismuth, and the six platinum metals are claimed to be available with total impurities ranging from 2 to 50 ppm. The present small and scattered world supply of so-called "pure" iron holds an unimpressive place in another group of 16 metals having approximately 100 ppm of foreign material. Of about 20 less rare metals, only the platinum metals are more costly to prepare. While the production of such rare varieties of iron may appear insignificant in the presence of thousand-ton operations with 95 to 99 pct metal, it must be emphasized that all researches on commercially interesting irons and steels are in fact studies of the modifications of the properties of iron by additional materials. Until the properties of high purity iron are directly measured, all ferrous research must operate without known base values. Traces of impurities may affect the properties of a metal in many ways. Infinitesimal traces of solutes, by disturbing the electronic configuration, greatly change the electrical properties of transistors and semiconductors2-3 and slightly larger traces might alter these quantities in iron. Soluble impurities which disturb the perfection of lattice arrangement not only may alter the magnetic constants and electric properties, but by their close association with dislocation phenomena probably control the very existence of the "yield point"; determine the value of yield stress; and perhaps control the selection of slip and cleavage planes. It has been speculated that impurities might even cause the allotropic transformation in iron, but in any case their rearrangement must contribute to the unreliability of heat capacity and other thermodynamic measurements. Impurities which do not remain in solution may cause even greater effects on the properties. Microscopically visible amounts of phases other than ferrite can be found in all high purity irons which have come to my attention. It can be calculated that from 50 to as little as 2 ppm of an insoluble material might be sufficient to completely film all grain boundaries in irons having grain sizes from ASTM Nos. 10 to 1. Should this occur, such films, even though invisible, may be very important in fracture problems, especially at extremes of temperature:' Studies of grain growth and diffusion normally imply consideration of a single-phase system, hence, in the presence of insoluble impurities they can be expected to give ambiguous data." High purity iron is also in demand for use as chemical and spectro-chemical standards; for work in classifying the lines of the iron spectrum; for biological work in nutrition; and for work in nuclear physics. where the presence of some sensitive

Jan 1, 1954

By T. D. Murphy, G. V. Henderson

The element silicon, with its usual partner, oxygen, plays the same role relative to inorganic materials as carbon and hydrogen play with respect to living organisms. The crystallographic structure of silicon dioxide (SiO2) consists of one atom of silicon well-nigh inseparably bonded to four contiguous atoms of oxygen, a gas of but slightly more than half its atomic weight, forming a three-dimensional network of SiO4 tetrahedra (Dietz, 1968). This wispy arrangement is the fabric of the mineral quartz which is one of the harder, more abrasive, and chemically stable raw materials to be found in Mother Nature's cupboard. Most of us are vaguely familiar with the observation that nearly 60% of the lithosphere to an approximate depth of 10 miles is composed of these two elements, which proportion actually rises to about 75% if the atmosphere, hydrosphere, and biosphere are included (Parker, 1967). Elemental silicon is a brittle steel-gray metalloid with a density of 2.42 and does not occur in nature. In its limited commercial form, which is still brittle and metallic in appearance, its density drops to 2.33. It combines with oxygen to form the gaseous oxide SiO, or the solid dioxide Si02 (analogous to its congener carbon in CO and CO2); a tetrachloride SiCI4 (analogous to CC14); or, combining with oxygen and one or more metal ions, forms the largest rock-making family of all, the silicates. Further, next to the feldspars, quartz is the most abundant known mineral and, in some form or another, accounts for roughly 12% of surficial terrestrial rock. It is this so-called "free silica" to which your attention is chiefly directed in this chapter. In any such consideration of silica, its several crystalline phases with their attendant differing physical properties appear worthy of delineation. Alpha quartz is the only one of this interesting polymorphic family that is thermodynamically stable at normal pressures and temperatures up to about 573°C. The low phases of tridymite and cristobalite can exist in the so-called metastable state below 117° to 200ºC but seldom occur in nature in these two different crystal forms (Sosman, 1965). Opaline silica, now considered by most researchers to be a variety of cristobalite, occurs in abundance and is the only exception. The three remaining polymorphs, keatite, coesite, and stishovite, also are metastable under ambient conditions. Keatite, however, is not known to occur naturally and has only been synthesized in the laboratory. The other two have been identified in submicron sizes and in microscopic amounts, occurring naturally as a result of high order shock-wave pressures generating quite elevated temperatures --such as might accompany the impact of a large meteorite on a hard sandstone terrain (Chao et al., 1962). An intriguing characteristic of these silica minerals, and one which has very practical applications, is their extremely variable densities. The classic 2.65 specific gravity of alpha quartz drops to 2.20 in tridymite, cristobalite, and lechatelierite (natural silica glass), as well as in many man-made glasses of commerce which are merely noncrystalline or amorphous solids in the form of super-cooled liquids which can no longer change their shapes (Pauling, 1950). It rises again to 2.50 and 2.93 for keatite and coesite, respectively, and finally becomes a reported 4.35 for stishovite-nearly a 50% range in density for the known physical combinations that silica naturally assumes (Frondel, 1962; Konnert et al., 1973; Pecora, 1960). Pursuing its esthetic aspects, briefly, silica is well-represented among gem stones which, to qualify as such, must have the attributes of beauty, durability, and rarity (Jahns, 1983). As quartzose gems usually have but one or, at

Jan 1, 1983

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 Theron Wasson

Michigan's production of 17,301,000 bbl. in 1945, which is in line with previous years, has been maintained by extensions to old fields like Deep River, Adams, Fork, and others. There were a number of new discoveries but, as in the past, these are not given very much importance because enough drilling has not been done to develop their potentialities; however, judging by the past, some of them will develop enough production so that 1946 -will probably be in line with other years. Activities in Michigan were confined to the Basin area of the lower Peninsula, which has been under development since 1925.

Jan 1, 1946

By L. Weyher, H. L. Lovell

This discussion is restricted to a very specific application of the cyclone - its use as a hydro-cyclone in the cleaning of fine coal. It is hoped that the development of the present data will assist in the further elucidation of existing qualitative models, and also in an enhanced application of the hydrocyclone and provide a base for further research. Discussed are the mechanisms of gravity separation in hydro-cyclones, test procedures, experimental observations, and industrial applications from these studies. Within the general area of unit operations, a considerable effort has been expended in theoretical and empirical research associated with cyclone operations. The motivation involves the industrial requirement for devices and techniques to manipulate small particles at low operating costs, a situation required in coal preparation. There are good reasons why the cyclone helps to satisfy this demand, because it combines operational simplicity (no moving parts) with versatility and high throughput capacity per unit area. The cyclone is one of the most widely applied tools in the process technologies. There are areas for potential cyclone application which have been only meagerly explored or not considered at all. This discussion is restricted to a very specific application of the cyclone - its use as a hydrocyclone in the cleaning of fine coal. It represents an initial presentation of a more comprehensive report. Coal preparation can appropriately claim the hydrocyclone since most of its predominant industrial uses have originated in this area and have spread into other applications, including the broad field of ore dressing, the petroleum industry, chemical processing, nuclear engineering and food technology. There is one operational principle common in all cyclones: A fluid is tangentially introduced into a cylindrical or conical container under pressure. A predominantly irrotational flow field1 is established within the cyclone (Fig. 1). The uniqueness of this flow is indicated by the variation in tangential velocity across the cyclone radius, which reaches a maximum a short distance from the center and decays toward the cyclone wall. In contrast, the tangential velocity in a centrifuge increases uniformly toward the wall. Usually two products are discharged from the cyclone. They differ in that one discharge consists predominantly of that portion of the feed fluid which moves along the wall axially away from the feed inlet, while the other consists predominantly of fluid spiralling along the central regions of the cyclone, in an axial direction opposite to that of the wall current. Fig. 2 indicates these discharge points schematically. The latter product may be termed the vortex-product, since it is discharged with the central vortex-current. In the case of conical cyclones, the former product may be referred to as the apex-product. Although the names "over- and underflow" are widely used, many cyclones are operated from extreme angular positions thus the proposed terms are less ambiguous. The cyclone feed fluid can be laden with solid particles or nonmiscible fluid drops. Such a feed component is discharged from the cyclone, after some residence time, into the one or the other product. Yet, the orifice through which a particle will leave the cyclone is dependent upon a number of factors. These factors, in a statistical sense, determine the path of the particle within the cyclone. Thus, different separation phenomena are possible and different process results attainable by the controllable variation of the particle path. It is then, to attain a fuller understanding of this particle path, to which this study is ultimately directed. It is anticipated that the detailed study of the data being developed will allow further elucidation of existing qualitative models. However, the development of a quantitative description of cyclone operation in terms of a mechanism is not currently feasible. The flow conditions in a cyclone are not fully understood even for a pure fluid, without the added complexity of the inclusion of multiple size-density particles. It is hoped that the development of the present data will also assist in an enhanced application of the hydro-cyclone and provide a base for further research. Some practical applications drawn from the data are suggested. Cyclone operations have been classified according

Jan 1, 1967

By L. L. Handy

The most common method of identifying hydrocarbon-bearing strata in a well that penetrates many different formations involves measurement and interpretation of the electrical properties of the formations as determined by electrical logs. Even though this method is used extensively, and even though in a great many instances it is capable of indicating presence of oil or gas, situations arise for which it is extremely difficult, if not impossible, to deduce the presence of hydrocarbons. These situations may involve the following. 1. A thin formation, bounded by highly resistive formations, in which it is impossible to obtain the actual resistivity of the uninvaded zone with existing logging devices. 2. A formation in which invasion has been so extensive that a value for the uninvaded zone resistivity cannot be obtained. 3. A very shaly formation in which the resistivity index, I, is lower than that usually associated with productive formations. 4. Laminated formations comprised of thin productive sands separated by thin shale streaks in which the individual sand and shale streaks are too thin to permit measurement of uninvaded-zone resistivity with existing logging devices. 5. Productive formations in which the water saturation is high. To extend the utility of electric log interpretation to identification of hydrocarbons in all types of formations, there is strong incentive to find a method not subject to these limitations. Some time ago, in connection with research on the wettability of reservoir rock, an investigation was conducted in which the resistivities of cores were measured shortly after they were removed from a core barrel, and again after they had been extracted and restored to their original oil and brine saturation.' The resistivities after extraction were generally lower. Other tests made on the cores indicated that they were more nearly water wet after they were extracted; thus, it was assumed that the observed changes in resistivities were due to a change in wettability of the cores. Other experiments'," have shown that resistivities of rock samples are sharply dependent on wettability. These experiments have shown that oil-wet samples are more resistive than water-wet samples. To obtain an understanding of how the wetting properties of the surfaces of core material affect electrical resistivity, a series of experiments was conducted. Two groups of core samples were prepared for testing. One group contained brine, but no residual oil. The other group was saturated with brine, flooded with oil to a low water saturation, then flooded with brine to a final residual oil saturation. Resistivity measurements were made on each group. Both groups were then flooded with the original brine to which a chemical had been added that renders sand and clay surfaces preferentially oil wet, a so-called reverse-wetting agent. very little change in resistivity was observed in cores containing only water. The group containing residual oil, however, showed resistivity increases of 100 to 200 per cent. These experiments showed that the resistivity of a core containing oil could be altered by changing wet-tability of the core. Moreover, the possibility was introduced that reverse-wetting agents might be employed as the basis for a logging method for identification of oil-bearing strata. Since behavior of a porous rock containing gas and water might be expected to be similar to that of a rock containing oil and water, such a method should also be applicable to identification of gas-bearing zones. In principle the wettability of the invaded zone could be reversed without altering conductivity of the interstitial water or the hydrocarbon saturation therein. Those strata showing significantly increased invaded-zone resistivities would, therefore, contain hydrocarbons; those with no significant change would be filled only with water. Addition of a reverse-wetting agent to a hydro carbon -bearing zone which is, by nature, already preferentially oil wet would not result in an enhancement of its resistivity. It is generally believed, however, that most hydrocarbon-bearing strata are preferentially water wet.

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10' to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970

By H. Kenworthy, R. B. Fisher, R. G. Knicherbocker, M. M. Fine

The progress made to date in the mineral dressing of complex Arkansas titanium ores is reported in this paper. Concentrates of rutile, a dioxide of titanium, were produced by treating a submarginal ore from the Magnet Cove Rutile Co., Inc., Magnet, Ark. The rutile recovery at present is 45 to 50 pct of the total TiO2, with the possibility of increased recovery with additional research. The work reported herein is part of a general study which will later include results of investigation of other titanium ore bodies in the Magnet, Ark., area. The fragile character of the rutile minerals, the softness of the gangue, the occurrence of pyrite and leucoxene, and the considerable proportion of extremely small size rutile in the presence of montmorillonite- and illite-type clays in the Magnet Cove open-pit mine are the important factors in the mineral dressing of this submarginal rutile ore. History The occurrence of titanium minerals in the Magnet Cove area of Arkansas was recognized as early as 1890, but it was not until about 1912 that any appreciable prospecting for the minerals was undertaken. At that time drilling was begun, a shaft was sunk, and several drifts were driven, but beneficiation to recover the titanium minerals was not attempted. The only successful mining and milling operation of the Magnet Cove rutile deposit was begun in 1932 by the Titanium Corp. of America and continued until 1942. The ore was washed by means of a rotary scrubber and then deslimed in a drag classifier. The discharge was ground in a rod mill, classified, and tabled to recover a rougher rutile concentrate, which was screen-sized and retabled on cleaner tables. The cleaner concentrates were given a reducing roast, screen-sized, and magnetically separated to produce a finished rutile concentrate. Most of the rutile produced during this period was sold abroad. In 1942, the Titanium Alloy Corp. of Arkansas (a subsidiary of the Titanium Alloy Manufacturing Co. of New York) purchased the property and rebuilt the mill. Subsequently, the plant and property were acquired by the Magnet Cove Rutile Co., Inc., of Little Rock, Ark., the present owners. Very little titanium has been produced since 1942. Although the Titanium Corp. activities yielded enough returns to allow continued operation for approximately 10 years, certain factors must be recognized. These are: (1) production of rutile in that period was during a low in the economic cycle which permitted low-cost operation on a small scale, and (2) a considerable portion of the production was above the water level and no drainage problems existed. Prior to this paper there has been no published report of any mineral-dressing investigation of the lower levels of the ore body. Reference is made in another paper1 to an earlier investigation of Magnet Cove rutile by the Rolla laboratory, in which it is stated that recoveries of 12 to 17 pct of the rutile were obtained. The present investigation was undertaken to improve the known milling processes and to provide adequate metallurgical information about the ore treatment. Titanium Technology The titanium mineral of primary interest in the present investigation was the titanium dioxide, rutile. Rutile is one of the industrial minerals whose annual consumption is relatively small but strategically important. The domestic production of rutile was 7100 tons in 1948. The imports of rutile in the same year were approximately 8000 tons.2 A major use of rutile is in the production of welding-rod coatings, for which a product containing a minimum of 92 pct titanic oxide is desired. Other constituents, such as lime, silica, and sulphur, must be held to a minimum, but hard-and-fast specifications for these elements cannot be drawn. It is necessary to incorporate the rutile in a welding-rod coating, make a sufficient number of test welds, and then determine the tensile strength of the weld metal in the as-welded and stress-relieved conditions. Such a test gives

Jan 1, 1950

By William C. Sleppy

The nmgnetic susceptibility of heat-treatable aluminuin alloys is sensitive to chanyes such as solution or dissolution of solute and the precipitation of mew phases. By measuring the change in the magnetic susceptibility of aluminum alloys caused by various heat treatments, an empirical relation was found from which atomic arrangements in dilute binary alloys of copper, zinc, and magnesiutn in aluminum have been delineated. The relation predicts the ultimate formation of C1LA12 when copper is precipitated from solid solution in aluminum. Euidexce joy silovt- range order is found for copper in solid solution in aluminum in the sense that copper atoms avoid being nearest neighbors to an extent greater than would result from a purely random arrangertzeizt. Hume-Rothery has predicted such short-range order joy solid solution of copper in aluminum The Al-Zn system agrees with evidence obtained from X-ray scattering at small angles and predicts a tendency for zinc atoms to cluster in solid solution in aluminum. In the Al-mg system, the empirical relation indicates an approach to randor distribution of magnesium in solid solution in aluminum with a tendency for magnesium segvegation which increases with incveasing temperature. ThE magnetic properties of metals are complicated by the fact that contributions are made to them both by electrons of a "metallic" type which belong to the crystal as a whole, and by electrons in states localized on particular atoms. An expression1'2 for the bulk magnetic susceptibility of aluminum may be written as the sum of three contributions: where XA1 is the bulk susceptibility of aluminum per gram of material (in the cgs system, the units are those of reciprocal density); Xa1+3 is the diamagnetic contribution of the electrons localized in ion cores; Xa1 is. the paramagnetic spin contribution of conduction electrons often called Pauli paramag-netism: Xa1 is the diamagnetic contribution of the conduction electrons often called Landau diamag-netism. Ion core diamagnetism arises from the precession of the electron orbits which occurs when a magnetic field is applied to a system of electrons moving about a nucleus. Its contribution to the magnetic suscepti- bility is small, temperature-independent, and unaffected by alloying. The conduction electron diamagnetism is also temperature-independent and arises from the translatory motion of the electrons. For perfectly free electrons this contribution should be exactly one-third of the Pauli spin paramagnetism, but this relation is seldom even approximately true. Blythe2 determined the conduction electron diamagnetism in pure aluminum and found it to be extremely small. Any change in the conduction electron diamagnetism caused by alloying is neglected in this work. The Pauli paramagnetic contribution3 to the magnetic susceptibility of aluminum depends upon the number of electrons that occupy excited states and whose spins can be turned parallel to an applied magnetic field. The number of electrons free to turn in the field is proportional to the temperature and each spin contribution to the susceptibility is inversely proportional to the temperature. A slight temperature dependence of Pauli paramagnetism occurs when the number of electrons occupying excited states cannot increase sufficiently to balance the inverse dependence on temperature of each spin contribution. The decrease of the magnetic susceptibility of aluminum with increasing temperature is attributed to a temperature dependence of the Pauli paramagnetism. Estimates of the Pauli paramagnetism of aluminum have been made by several workers.2,4,5 All of the values are in reasonably good agreement with each other. In this work Xal at 17°C is taken as 0.761 X 10-8 cu cm per g. An expression similar to [I] can be written for the magnetic susceptibility of an aluminum base alloy containing a fractional weight percent x of solute:' Xa = (1 -x)XAl+3 +xXsoluteion * XaPauli +Xadia) [2] where X, is the magnetic susceptibility per gram of alloy, Xal'3and Xsolute ion are the ion core diamag-netic contributions, and xpauli and xdia are the Pauli and diamagnetic contributions of conduction electrons in the alloy. If the components of a mixture are not alloyed but simply mixed together in their pure states without producing a new phase, then the magnetic susceptibility of the mixture is given by the Wiedemann additivity law: Xm =x1X1 +x2x2 + ..xnxp [3] where X, is the susceptibility per gram of mixture and xnXp are the weight fractions and susceptibilities, respectively,-. for the pure components. The additivity law is not applicable to alloys because the outer electronic structures of the components are changed by alloying.' Both the Pauli paramagnetism and Landau diamagnetism are affected; hence the magnetic susceptibilitv of an alloy is usually different from that calculated using the additivity law. In this work the difference, X, -X,, is taken as a measure of the change caused by alloying.

Jan 1, 1968

By D. W. Levinson, L. F. Mondolfo, N. A. Gjostein

MANY investigations are reported in the literature on the age hardening of Al-Mg-Zn alloys but most of them are concerned mainly with mechanical property changes. The present investigation was started to determine the structural changes in an AlMgZn alloy. The alloy composition was chosen in the existing phase diagram" so as to lie on the quasi-binary section Al-(AlZn)Mg Actually, it was found that the diagram as published was inexact at the lower temperatures and that the phase in equilibrium with aluminum at the lower temperatures is not the ternary compound. Technique The alloy used for the investigation was prepared from high purity materials and the resulting composition as determined by chemical and spectro-graphic analysis was: Zn, 6.17 pct; Mg, 2.13 pct; CU, 0.03 pct; Si, 0.009 pct; Fe, 0.005 pct; and the remainder, aluminum. An ingot -in. thick was cast, homogenized, hot and cold-rolled to strip 0.064-in. thick for dilato-metric and powder work, and to foil 0.005-in. thick for single crystal work. Solution treatment temperature for all specimens was 475°±5°C for periods of at least 1 hr, either in air furnaces or lead baths. Aging was done in oil or Pb-Bi baths controlled to within ±3°C. The aging was investigated at the following temperatures: room (30°), 130°, ZOO0, 260°, and 300°C. For the dilatometric study, the length changes were measured continuously, at temperature, using strips of alloy 10 in. long, shaped as channels to eliminate undesirable deflection due to bending. To compensate for thermal expansion and contraction due to the variations in the temperature of the aging baths, the dilatometers were built of the same alloy as the one being tested, with the same shape and size, but with material fully annealed. Gages on which 0.0005 in. could be read and 0.0001 in. estimated were used to measure the dilation. Length changes were also measured at room temperature. Strips approximately 10 in. long were solution-treated, quenched, and measured in a supermicrome-ter in which 0.0001 in. could be read and 0.00001 in. estimated. The specimens were immediately aged for a given time, remeasured, and then the cycle was repeated, including the solution treatment. The error of measurement with this technique was somewhat larger, but the results confirmed those obtained by continuous measurements. The sheet used for the dilatometric work was checked to determine grain orientation. Both X-rays and etching methods revealed a rather coarse grain size but only a negligible amount of preferred orientation. Thus, volume changes calculated from length changes are not invalidated by preferential orientation effects. Pieces of the sheet used for the dilatometric work were also used for the metal -lographic work. Filings for the powder X-ray study were produced from a homogenized piece of sheet. These filings were magnetically purged of iron, screened to 200 mesh, sealed in a Pyrex tube containing an argon atmosphere, and solution-treated. When quenching, the glass tube was broken, so that the powder dropped directly into cold water. After drying with alcohol, the powder was sealed into capillary tubes containing an argon atmosphere and then aged for the required times. In spite of all these precautions the three strongest lines of a( Al2o) appeared in all patterns, and were used as internal standards. By the use of these standards, accurate corrections for film shrinkage were obtained. For the back reflection patterns, annealed nickel powder was mixed with the specimen to act as internal standard. A preliminary investigation was made in small (57.3 mm diam) powder cameras. From these patterns the changes which took place in the solid-

Jan 1, 1957