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By Paul M. Tyler

YEAR after year, the kaolin industry of the United States has been setting new production records and making better products. High-grade paper, pottery, and rubber clays are produced in this country mostly in the South. Georgia alone contributes over 70 pct and South Carolina almost 20 pct of the total domestic output. Residual kaolin is mined in North Carolina, highly plastic but naturally sandy Tertiary (Eocene) potting clays are worked in north central Florida, and good white clays are produced in several other states, but the main sources of kaolin or china clay have been numerous deposits in the Tuscaloosa (Upper Cretaceous) formation. This formation of generally sandy sediments is called the Middendorf member in older geologic reports and corresponds in age with some of the New Jersey clays. As shown in fig. 1, it crops out almost continuously in a generally southwesterly direction across South Carolina and Georgia and into Alabama. Clay is mined from this formation in all three states but the principal producing centers lie within about 10 miles of a straight line drawn between Aiken, S. C., and a point about 10 miles south of Macon, Ga. The white kaolins of the South were recognized and used prior to the Civil War but suitable treatment processes were not introduced until World War I when imports, chiefly from England, were curtailed. Although imports of high-grade clays were resumed after 1918, the domestic industry managed to treble its prewar production record during the early 1920's and has continued to grow. Whereas the 1909 to 1913 average total production in the United States was only 132,104 short tons valued at $705,352 f.O.b. mines, the output in 1948 was 1,-568,848 tons worth $19,756,738. Paradoxically, it seems in retrospect that the early failure of the American industry to meet foreign competition was due to the superior quality of our sedimentary clays in their natural state. Kaolin, of course, is the principal decomposition product of feldspars which originate in acidic igneous rocks such as granite, aplite, alaskite, granodiorite, quartz porphyry, etc. English china clays occur in residual deposits and before they can be marketed they have to be treated to remove accompanying quartz, mica, and other impurities. Notwithstanding the relatively crude methods employed, the final product is a beneficiated clay which is subject to a certain amount of technical control as to quality and uniformity. Although the naturally concentrated deposits in Georgia and South Carolina contain some of the finest crude white kaolin in the world, even it can be made better by suitable treatment. In recent years well over half of the high-grade china clay produced in the United States has been used in making paper. Some qualities of paper clays are still produced by the dry process, or air flotation, but the paper industry's specifications have grown so exacting that wet processing was adopted and more refined methods had to be perfected. Notwithstanding notable advances in clay-preparation technology during the past decade, or possibly because these advances have implemented and encouraged technologic changes in consuming industries, demand has grown for products of higher uniform quality than can be obtained from even the best natural deposits without rigidly controlled fractionation. Largely as a result of the wide adoption of machine coating for paper, the clay industry has been obliged not merely to eliminate virtually all mineral impurities but also to segregate the clay substance itself into narrow particle-size ranges. By extraordinary coordination of sales effort and production technology, several Georgia companies manage to market a wide variety of specialized joint products but the commercial success of many producers depends upon their mining only the best parts of their deposits and then skimming the cream of this almost pure clay in order to obtain a maximum yield of kaolinite finer than about 2 microns in maximum particle size and possessing low viscosity as well as the more familiar attributes of suitable color and brightness, or reflectance. To the casual visitor from another mineral industry, the kaolin mines and plants may appear to be

Jan 1, 1951

By Henry F. Adams, Guy H. Ruggles

In this paper the authors aim to chronicle the experience and salient points brought out in changing flotation reagents at a concentrator which had probably been using a minimum amount of oil at a minimum cost per ton, to a more complicated system requiring a partial chemical control. The original oils were coal tar and pine oil. The new reagents are lime, xanthate and pine oil. It was found that there were no insurmountable difficulties and eventually the cost of the new reagents per ton of ore proved to be very little more than that of the old. Lime Plant When the question of handling lime came up there were two propositions open: (1) to handle the lime dry; (2) to handle it wet in the form of an emulsion. Granting that a dry lime feeder would function properly, delivering lime uniformly, the chief objection was the dust that would be raised when these feeders were being charged or operated, as the only possible location was on a gallery beneath which men were working. With this objection the handling of lime as an emulsion seemed to be the better scheme. The lime plant which was first installed was for experimental work on one section. This was gradually changed and developed until it was of sufficient size to accommodate 20 sections. The various changes will not be discussed and the following description deals only with the fully developed plant. Crude as it is, and perhaps somewhat expensive to operate, the lime-handling plant has been quite successful. Much has been learned which will pave the way for a better installation in the future. Burnt lime is received loose in standard gage box cars. This is the product of the kilns and has had no screening or sorting. A grab sample is taken from each car as it is unloaded. An average of the analyses of samples from 44 cars gave the following: Available CaO Total CaO, Oxide and Hy- MgO, Fe²O³ + Al²O³, Insoluble, Per Cent. drate, Per Cent. Per Cent. Per Cent. Pek Cent. 88.3 79.2 1.6 ' 1.3 2.2

Jan 1, 1928

By Robert I. Jaffee, Bruce W. Gonser, Eugene M. Smith

There has been little investigation of the gold-germanium binary alloys. Haughtonl does not mention any work on the system. In a review article commemorating the fiftieth anniversary of the discovery of germanium, E. Einecke2 mentioned a gold-germanium eutectic at 24 atomic per cent Ge (10.4 weight per cent) melting at 359°C., but did not give the source of his information. From measurements of electrical conductivity, J. 0. Linde3 estimated that at least 0.6 weight per cent germanium is soluble in gold. The recent availability of germanium in this country in commercial quantities has led to interest in its properties and its alloys. This study is part of a program of investigation on germanium alloys; work on ternary alloys involving germanium and gold will be reported later. In this investigation, the composition and melting point of the Au-Ge eutectic reported by Einecke has been found to be substantially correct. Eutectic composition has been placed at I2.0 per cent germanium, however. An alloy of 10.4 per cent Ge, Einecke's value, was found to have a few gold dendrites in it. The cutectic temperature has been determined as 356.0 6 ± 0.5°C., slightly less than the temperature of 359°C. reported by Einecke. The liquidus curves and the solid solubility of ger- manium in gold have been determined, and are shown in Fig. I. Materials and Alloying The germanium used in this investigation was prepared by the Eagle-Picher Lead Co. from pure germanium oxide, by reduction in clay crucibles with sodium cyanide. The regulus is quite pure, assaying over 99.9 per cent Ge. High-purity gold obtained from Handy and Harmon was used. Alloying was carried out in graphite crucibles in an atmosphere of purified hydrogen. The temperature was brought up to 1050" to iioo°C., and the metal was allowed to freeze in the crucible. Prepared in this way, the gold dendrites in hypoeutectic alloys were somewhat segregated at the bottom and sides of the ingot, and on the hyper-eutectic side the lighter primary germanium tended to gather at the top. Most of the alloys were made from virgin metal. Low-germanium heats were made by alloying pure gold with the eutectic. Melting losses were consistently a few milligrams or less, and the composition could safely be taken from the intended analysis. The 30 per cent and 50 per cent germanium heats for thermal analysis were made in part from remelted higher germanium heats, and they may be OR composition as much as one per cent. Because of the high cost of materials, the weight of heats for thermal analysis were 15 to 20 grams and heats for metallo-graphic, X-ray, and hardness specimens were 2 to 4 grams.

Jan 1, 1945

By J. S. Bryner

In the study of metallographic specimens in the electron microscope, there is need for a method of locating the same field in both the light microscope and the electron microscope. This need arises chiefly from the fact that in the electron microscope the magnification and degree of resolution are so much higher, and the field so much smaller than in the light rnicroscope that it is often difficult, if not impossible, to identify positively what is being observed. The difficulty is increased by the fact that, because a transparent film replica of the metal surface must be used in the electron microscope, micro-constituents can be identified not by their color but only by their texture and contours. For these reasons it is desirable to obtain a series of photographs showing the same field in both microscopes in order that the appearance of common microstructures and micro-constituents in the electron microscope may be identified and catalogued for future reference. The need for a method of locating the same field in both microscopes arises also when it becomes desirable to enlarge in the electron microscope for more detailed study a particular interesting structure observed in the light microscope. Using the standard polystyrene-silicalJ replica technique, in which the silica film replica is fished from the ethyl bromide on a 1/8 in. diam zoo-mesh specimen screen, the possibilities of locating a particular area on the film in the electron microscope are rather remote. The desired structure may be obscured by the wires of the specimen screen or unrecognizable at the high magnification. A solution to the problem would be provided if a specially designed specimen screen, containing an opening which could be absolutely identified and quickly located in the electron microscope, could be fastened to the silica film replica in such a position that the desired field on the specimen would be located at the identifiable opening in the specimen screen. The design for such a specimen screen, a method for producing it, and a technique for fastening it to the silica film replica are described below. Description OF Method The Specimen Screen A simple design for a specimen screen containing an opening easy to identify and locate in the electron microscope is one with two lines of openings at right angles in the form of a cross. Such a screen is shown in Fig I. The opening at the center of the cross is identified easily and can be located quickly in the light microscope and in the objective image of the electron microscope. The specially designed specimen screens for this work were produced in quantity by electroforming. On both sides of a polished strip of copper I X 3 X 1/8 in., twenty patterns of the cross of openings were punched with a diamond point micro-hardness tester, using a load of magnitude

Jan 1, 1949

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. 'This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By T. Egleston

circumstances, would prefer the steel with which they are now familiar, to a specimen that Mr. Sandberg has described as having broken into seventeen pieces under the wheels. After blowing such low manganese steel, it may be coaxed into a rail, but it is a wonder that it holds together so long as it does, with so great a nornber of minute flaws. I would not in any way depreciate chemistry, but I think it should be kept in its proper sphere. Let the chemist look after the quality of pig metal, and apply common sense in the avoiding of extremes, then the most fastidious railroad cannot find fault with the result. PROFESSOR EGLESTON, New YORK City : It is not my place as an engineer to apologize for the chemists, but as no one seems disposed to do so, and as they have had more than their share of criticism, 1 am glad to say that I believe there are chemists in this Institute whose work and word are just as reliable, arid perhaps even more so, than that of the average engineer. But we ought to make a distinction; there are chemists and chemists. With the ordinary commercial chemist, who looks upon the science as so much merohandise, I have not a particle of sympathy; but with the chemist who looks upon his profession as engineers do upon theirs, I have every sympathy. When matiufactorers and engineers go to a chemist and ask him to make an investigation, and scretv him dowu to the lowest point, turning the equivalent of his brains into cents and mills, they ustially get an exact equivalent in poor work for miserable pay, and no one has or should have any sympathy with them, and the under these conditions has no right to ask for any, and no reason to criticise any work that he may get under such circumstances. But I am disposed to think that the chemists who have been replwented and discussed at this meeting do their work conscientiously, and that it is as reliable as that of almost any profession. I believe, however, that this problem of steel rails is being investigated in a wrong direction. I said so at the Pittsburgh meeting, and I think the discussion of this meeting will prove it to all those who have heard it. I think the chemigt is incapable of solving this problem unlees he goes very far into the domain of physical chemistry, so far that it becomes physics and not chemistry; and that the physicist will be the one on whom we must rely in the future for the elucidation of the subject. The chemist may aid the physicist, but it is my decided opinion that we are looking in the wrong place to get the explanation of the phenomena.

Jan 1, 1881

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. 'This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By Don B. Carson, Donald L. Katz

NATURAL gases under pressure form crystal-line hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methane-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbonrich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. INTRODUCTION Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villard1 and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies.2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Deaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on temperatures and pressures of hydrate formation for pure methane, ethane, propane, n-butane, methane-ethane mixtures, methane-propane mixtures, methane-butane mixtures, and some 15 natural gases, all in the presence of excess water. However, up to the present time no method has been available for predicting the temperature at given pressures or the pressure at given temperatures at which natural gases will form hydrates if saturated with water. This paper pre¬sents data on the methane-propane-water, methane-pentane-water and methane-hexane water systems in four phases, one of which is the hydrate. The application of the phase rule to the methane-propane-water data proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1941

By R. P. Carreker, J. G. Leschen, J. H. Hollomon

THE external appearance of a crystal which has undergone plastic flow suggests that adjacent blocks of the crystal have glided bodily past one another along the slip planes. However, the great discrepancy between the shear stresses calculated to effect such a movement and those actually observed has for many years stimulated searches for more satisfactory interpretations of the slip process. Appreciable success in these efforts has been realized by assuming the presence in the crystal of various sorts of imperfections and by considering the consequences of the presence of these flaws when stress is externally applied, The theory that has received the most attention recently-that of dislocations-postulates the occurrence of small, mobile imperfections or dislocations which move through the crystal along the slip direction, each dislocation being attended by a local shear displacement of one interatomic distance. Thus only that portion of the crystal through which the dislocation has passed may be said to have slipped, Since each dislocation produces a displacement of only one interatomic distance, an avalanche or train of many dislocations would be necessary to account for the observed displacements of several hundred or thousand interatomic distances. The salient point of the theory of dislocations is the concept that a slip band does not suddenly appear in its entirety. On the contrary, it grows progressively across the slip plane as the individual dislocations successively appear and advance in a train through the crystal. However, the concept of growth is not intrinsic only to the theory of dislocations, since atomistic mechanisms other than that postulated by the dislocation theory can quite probably also describe the growth of a slip band. For instance, a slip band might resemble a disc-like interface that appeared and then grew continuously from a small size, producing a displacement that increased with the size of the disc, Whatever the precise mechanism, the concept of growth is in itself consistent both with -the observed low values of critical shear stress and with the experimental observation that slip bands. frequently do not traverse the entire crystal. The likelihood that slip bands grow implies that they must first be nucleated and that the initiation of slip can therefore be analyzed in terms of the general concepts of nucleation. Indeed, this suggestion was advanced1 several years ago, but the matter does not appear to have been further pursued. Recent advances in the theory of nucleations2,3,4 have encouraged such a treatment of the slip process. As will presently be demonstrated, this approach to the problem not only accounts successfully for the incubation periods that have been observed5,6 to precede slip but also predicts certain transient effects in the deformation process, The existence of these transients apparently has not hitherto

Jan 1, 1948

By R. DiBella, H. Biloni, G. F. Bolling

A study of the detailed relationship between solidification substructure and microsegregation in dilute tin alloys has been continued. New observations reveal that depressions form at the solid-liquid interface not only as an initial form of segregation but throughout the range of increasing constitutional supercooling. In order to show the importance of this node formation it proves convenient to make two simplifications. Although substructure changes continuously as constitutional- supercooling increases,&apos; the following discrete stages may be used for discussion: 1) the planar solid-liquid interface; 2) ordered nodes, or depressions at the interface;&apos; 3) two-dimensional or elongated cells;3 4) regular or hexagonal cells;4 5) distorted cells, or hexagonal cells with branches;4 6) dendrites. It is also convenient to ignore observations made near grain boundaries which interact with the cellular substructure.2-4 And, it should be clearly pointed out that all singular depressions at the solid-liquid interface will be called nodes. Heretofore, the term "node" has been used without clear justification to describe both the truly isolated depression and the junction of cell walls appearing in a later stage of segregation. This usage is continued because it seems proved by the observations. Standard systematic growth of tin crystals was undertaken over a broad range of constitutional supercooling using various added solutes. Except for one or two chance observations, this research failed to reveal any appreciable range of growth conditions over which a disordered array of isolated nodes exists. Even though &apos;some finite range of random instability must exist, it is now concluded that stage one passes very rapidly to stage two. Next, after confirming that stage two passes to stage three by the elongation of isolated nodes: a reexamina-tion of stages three, four, and five followed. Standard metallography showed that pockets of higher solute concentration (for ko < 1) became more numerous in cell walls the more severe the growth conditions. These high-concentration regions must arise from depressions; however, in stage three their segregation is not distinguishable from the segregation of the nodes which join cell walls together. It seems, therefore, that the presence of nodes is causal in the formation of new cell walls, and that the mechanism by which stage three passes to stage four is initiated by nodes. If a similar reasoning is followed, the separation of stage four from stage five appears to be just a convenience that has arisen from the decanted interface observations made in the past. The present observations again show that more severe growth conditions relate directly to an increase in the number of nodes in the hexagonal cell walls. These nodes apparently serve as the origin for lines of segregation extending within the body of a cell, and can thus be assumed to represent the earliest form of branching,* as shown here in Fig. 1. The examination of stage six involved decanted-interface structures as in Fig. 2, which are similar to those considered by Rutter and Chalmers,5 Plaskett and winegard,6 and Hellawell and Herbert,7 and where distinct protrusions are each surrounded by a depressed boundary. The corresponding microsegregation behind the interface, but not far enough behind to allow a smearing of the segregation because of diffusion,4 is shown in Fig. 3. Both the shape of the decanted interface and the segregation pattern behind it

Jan 1, 1968

By J. E. Burke, A. M. Turkalo

IN 1923 Desch¹ pointed out that the grains in a metal which is anisotropic with respect to its thermal coefficient of expansion would contract differently upon cooling, and that the stresses developed might approximate the plastic strength of the metal. More recently Boas and Honeycombe2-5 studied the behavior of several metals upon thermal cycling and observed that the stresses developed in arlisotropic metals are great enough to produce slip lines in individual grains and a roughening of the specimen surface. This phenomenon they have named "thermal fatigue." The mechanism they propose involves essentially a kneading of the grains, the deformation being alternately in compression and tension in a given grain as the temperature is changed in one direction and then the other. The present work was undertaken to investigate the possibility that an additional mechanism might operate to produce plastic deformation during thermal cycling—a "thermal ratchet" that depends upon a combination of grain boundary flow to relax the stress that develops between differently oriented grains upon raising the temperature and transcrys-talline slip to relax the oppositely directed stress which develops on lowering the temperature. Thus, thermal cycling should produce a nonreversible distortion such that certain grains will change shape differently from their neighbors with a simultaneous displacement being produced at the grain boundary. Temperature Dependence of Grain Boundary and Grain Strength The critical resolved stress for the initiation of slip in metal grains is only mildly affected by temperature." For example, in cadmium it decreases from 0.15 to about 0.05 kg per sq mm when the temperature is increased from 20° to 458°K and further temperature increase causes little further decrease. On the other hand, the work of KG1 indicates that the grain boundaries behave in a viscous fashion that can be described8 by the expression: t = BVexp(Q/RT) [1] t is the shearing stress on the boundary; B, a constant; V, the flow rate at the boundary; Q, the activation energy for grain boundary flow; R, the gas law&apos;s constant; and T, the absolute temperature. Eq 1 indicates that the stress necessary to cause a given grain boundary flow rate, V, decreases rapidly with increasing temperature. The value of the constant B is such that at sufficiently low temperature and ordinary strain rates deformation will occur preferentially by slip rather than by grain boundary flow. There is considerable evidence to indicate Consider the bicrystal shown in Fig. 1. In grain 1 the slip plane lies 45 " to the boundary while in grain 2 the slip plane is 90" to the boundary. The coefficients of expansion of the grains in a direction parallel to the length of the crystal are a1 and a, with a, > a2 for the orientations shown. The sequence of events that can occur upon heating and cooling this specimen is illustrated schematically in Fig. 2. Initially there is assumed to be no stress in the specimen (A). Upon heating, grain 1 attempts to become longer than grain 2, but is constrained by grain 2. Thus grain 1 is loaded in compression and grain 2 is loaded in tension, and a shearing stress is present across the boundary (B). As the temperature is increased, the stress will build up, and finally grain 1 will be plastically deformed by slip, since the greater stress is resolved on its slip planes. Any further heating will result in more slip and the stress will remain constant until some temperature T* is reached where the stress can be relaxed by grain boundary flow.† At this relaxation temperature (C) a step will appear between grain 1 and grain 2. Further heating above T* will cause grain 1 to become relatively longer, but no stress will appear because the grain boundary is too weak to support the stress (D). Upon cooling again, at T* (E), the grain boundary will again be able to support a shearing stress, and upon cooling further, grain 1 will be loaded in tension and grain 2 in compression (F). When the decrease in temperature below T* is sufficient to impose the critical shear stress upon the slip plane of grain 1, it will be stretched by slip.

Jan 1, 1953

By A. Kenneth Schellinger

THE terms surface tension .and surface energy are well known when applied to liquids and are generally described by referring to the excess energy of the air: liquid interface as a result of unsaturated molecular forces surrounding the surface molecules of the liquid due to the presence of the air phase on one side. Such unbalanced forces produce the familiar water droplet of spherical form and are generally summed up as a surface tension measured in dynes per centimeter which can be shown mathematically to be equal numerically to a corresponding surface energy expressed in ergs per square centimeter. A specific surface energy, however, is best thought of as the energy necessary to produce one unit of new surface on a substance. Hence, in producing a bubble in a flotation cell the impeller must supply surface energy corresponding to the air: liquid interfacial area on the interior of the bubble. Inasmuch as it is relatively easy to extend or contract the surface of a liquid, there are a number of successful methods for liquid surface tension, or energy, measurement based upon surface deformation. This happy state of affairs does not, however, extend to solids, which are considered to possess surface energies for the same reasons as do liquids, i.e. because of unsaturated ionic bonds at the solid gas interface. As in the case of the flotation cell producing surface on liquids as new bubbles, it takes energy to produce new surface on solids as new particles. As every mill man knows, this surface is produced on mineral solids in a grinding mill by the action of a tumbling mass of iron balls. But here so much energy usually is wasted by the inefficient action of these balls that a large amount of heat is generated, and the surface energy production may be easily confused with the energy necessary to produce this ineffective heat. The tumbling balls and fracturing minerals ultimately take their energy from a rather large electric motor. It has been variously estimated that from 10 to 20 pct" only of this energy from the motor does not appear as heat and may be presumed to appear as surface energy on the minerals present.. Such a production of new surface on the mineral phases is accompanied, of course, by a size reduction that is inevitable as more and more mineral interior molecules become surface molecules by the fracture exposure. This size reduction of mineral particles, although the most obvious feature and perhaps the sole object of the milling operation, is from this energy viewpoint the outward manifestation of the production of surface energy only. Measurement of the characteristic surface energies of pure minerals and their various mixtures in ores would be a step towards understanding of the energetics of the commercial grinding operation. In addition, the characteristic surface energy of a mineral is probably a physical property specific for that mineral, and therefore, from a scientific standpoint, should be measured. It is interesting to note that, in contrast to the large body of work on the surface tensions of liquid systems and biological systems, the field of solid surface energies has been neglected. Prior to. 1920 it is difficult to find more than one or two references to work on solid surface energies in Chemical Abstracts. Since 1920 such references number somewhat less than 100, while those on liquid systems are numbered in the thousands. Much of this apparent neglect of the field of solid surface energies (the term is intended to be somewhat inclusive at this point and refers both to the solid: gas, and the solid: liquid interface) is because of the lack of a reliable method of measurement rather than any lack of scientific curiosity. It was, and still is, difficult to produce new surface on a solid without the simultaneous production of interior changes in the same solid which may consume part of the energy used. The extension in the surface area can be measured, but the interior crystal-

Jan 1, 1952

By P. G. Shewmon, F. R. Winslow

An experimental method is describedfor Ihe determination of the derivative of the surface free energy (y,) with surface orientation using symmetric bicrystals. The method measures the equilibrium root-angle of grain boundary grooves for the same grain boundary on two different surfaces. In contrast to previous methods, the presence of annealing twins is not necessary. Results on silver at 900°C indicate that ??s/?3 is 0.014y, on the (loo), 0.075y, on the (111), and < 0.004?s on the (110). DURING an investigation of the kinetics of grain-boundary grooving on silver&apos; values of the derivative of the surface free energy ?s with respect to orientation were needed. Previous investigations of these so-called torque terms show that, for low-index planes in copper2 and nickel,&apos; a finite derivative exists even near the melting point. These two studies give the only previously published values of the torque on low-index metal surfaces. These investigators measured the equilibrium root angles, both greater than and less than 180 deg, along the lines where a twin boundary intersects a free surface. The technique described here is suitable for materials which do not have annealing twins, and enables the surface for study to be chosen instead of having to work in a direction normal to the twin trace on the surface. The purpose of this paper is to describe this new technique and to report the values found for the (111): (100), and (110) surfaces of silver. To check the technique proposed above, a series of 99.99 pct Ag bicrystals were used. These bicrystals were grown from the melt by a modified Bridge-man technique so that a low-index direction was parallel to the growth direction. Two orthogonal faces were studied on each bicrystal. One of these contained the low index or simple plane normal to

Jan 1, 1963

By Ivor Jenkins

Processes employing &apos;controlled at-mospheres in the heat-treatment of metals and alloys are now well established on an industrial scale, and the general principles involved and the advantages to be gained in the use of the technique have received considerable publicity over a period of years. During this time the greatest emphasis has been on the establishment of the process in industry, the main effort being devoted to development work on various types of atmospheres, their useful fields of application and the design of suitable heat-treatment furnaces in which they are to be used. The various types of controlled atmospheres are fairly well standardized, but there still remains a considerable field for the investigation of related problems, in connection with both the gas-generating equipment and the surface chemistry of the heat-treatment of metals, especially in complex controlled atmospheres. This paper describes certain investigations of this nature that were carried out in England up to 1939. The development of processes employing controlled atmospheres has been asso-ciated to a very large extent with the heat-treatment of steels, both because of the major importance of steel in industry and the many diverse and dificult prob-lems of surface chemistry involved when steels of such a wide range of composition are heated in the presence of active gases. Controlled atmospheres such as disso-ciated and burnt ammonia or charcoal gas are used in the heat-treatment of low-carbon and high-carbon steels, but from certain points of view a suitable atmosphere generated by the partial combustion of city gas is to be preferred. Both the ammonia derivatives are comparatively expensive, and even if the burnt ammonia is regenerated, thereby reducing operating costs, the capital expenditure of the gas plant may make it prohibitive for the smaller type of furnace installation. Charcoal-gas generators are not without their operating difficulties especially those associated with the quality of the charcoal, clinker formation and the removal of carbon dust from the generated gas. City gas has the advantage of being comparatively cheap and "on tap" in most if not all industrial centers. The use of raw city gas as a protective atmosphere in the heat-treatment of steels has been described,&apos; but it presents certain difficulties because of its complex composition and its explosive nature when mixed with air. These factors, together with the tendency toward sooting at elevated temperatures, arising mainly from the hydrocarbon gases present, all militate against its use as a protective atmosphere in industrial furnaces. The following analysis, based on the analyses of city gas in different localities in Great Britain, indicates the wide limits existing

Jan 1, 1948

By Ivor Jenkins

Processes employing &apos;controlled at-mospheres in the heat-treatment of metals and alloys are now well established on an industrial scale, and the general principles involved and the advantages to be gained in the use of the technique have received considerable publicity over a period of years. During this time the greatest emphasis has been on the establishment of the process in industry, the main effort being devoted to development work on various types of atmospheres, their useful fields of application and the design of suitable heat-treatment furnaces in which they are to be used. The various types of controlled atmospheres are fairly well standardized, but there still remains a considerable field for the investigation of related problems, in connection with both the gas-generating equipment and the surface chemistry of the heat-treatment of metals, especially in complex controlled atmospheres. This paper describes certain investigations of this nature that were carried out in England up to 1939. The development of processes employing controlled atmospheres has been asso-ciated to a very large extent with the heat-treatment of steels, both because of the major importance of steel in industry and the many diverse and dificult prob-lems of surface chemistry involved when steels of such a wide range of composition are heated in the presence of active gases. Controlled atmospheres such as disso-ciated and burnt ammonia or charcoal gas are used in the heat-treatment of low-carbon and high-carbon steels, but from certain points of view a suitable atmosphere generated by the partial combustion of city gas is to be preferred. Both the ammonia derivatives are comparatively expensive, and even if the burnt ammonia is regenerated, thereby reducing operating costs, the capital expenditure of the gas plant may make it prohibitive for the smaller type of furnace installation. Charcoal-gas generators are not without their operating difficulties especially those associated with the quality of the charcoal, clinker formation and the removal of carbon dust from the generated gas. City gas has the advantage of being comparatively cheap and "on tap" in most if not all industrial centers. The use of raw city gas as a protective atmosphere in the heat-treatment of steels has been described,&apos; but it presents certain difficulties because of its complex composition and its explosive nature when mixed with air. These factors, together with the tendency toward sooting at elevated temperatures, arising mainly from the hydrocarbon gases present, all militate against its use as a protective atmosphere in industrial furnaces. The following analysis, based on the analyses of city gas in different localities in Great Britain, indicates the wide limits existing

Jan 1, 1948

By Benj. N. Webber

There is a broad analogy between super gene nickel deposits and super gene copper deposits of the porphyry type. Some of the nomenclature of supergene copper may he applied to super gene nickel deposits. The obvious connection between lateritization and supergene nickel concentration requires some clarification of the nomenclature of laterite of ultrabasic rock parentage. Lateritization is a progressive process and the transition products of the laterite profile are a key to the process of nickel concentration since the profile grades from unaltered peridotite to the highly ferruginous ultimate laterite capping. This profile is formed under highly restricted geographic and geologic conditions. Faulting contributes to the formation and localization of the higher grade commercial segregations of nickel. That there may be auxiliary sources of nickel other than olivine is suggested. The volume of peridotite necessary to produce a unit of laterite at any point in a complete profile is calculated on the basis of the chromite content. The lixiviation, transportation, and precipitation of the elements involved is considered and the source of the reagents and chemical mechanisms are suggested. The role of sodium chloride is considered important. The progressive changes in the lateritic profile have an effect on the general process since lateritization takes place in overlapping environmental phases. The mineralogy of laterite and the redistribution of elements is illustrated by compositional curves derived from a completely mature laterite. Nickel scanvenged by iron oxides tends to be redissolved and moves downward to the zone of transitional magnesium silicates where it is reprecipitated. The geometry of the nickel enrichment zone is simple in general, but complicated in detail. Elongated pods of a greater concentration of nickel are indicated to be a reflection of faulting. Lateritization and concentration of nickel may be arrested at any stage and be modified by several factors.

Jan 1, 1973

By O. F. Kammerer, W. E. Miller, D. H. Gurinsky, J. Sadofsky, J. R. Weeks

Zirconium and titanium inhibit solution mass transfer of steels by liquid bismuth, mercury, and lead. It is shown that in bismuth and mercury, these adsorb on the surface of the steels and subsequently react with nitrogen and possibly carbon from the steels to form inert, adherent surface layers of ZrN, TiN, or TiN + Tic. Data are presented which describe the condition under which thase deposits form. These inhibitors decrease the solution rate of iron into bismuth, and require a higher supersaturation for precipitation of iron from bismuth. USE of the low-melting heavy metals (bismuth, lead, mercury, and their alloys) as coolants has been limited because solution mass transfer of steels occurs in these liquids; i. e., iron dissolves in the hot sections of the heat transfer circuit and deposits in the colder sections. The rate of solution of iron and the temperature coefficient of solubility are sufficiently great to cause complete or partial stoppage by the deposition in the coldest section of a closed circuit in finite time, even though the actual solubilities are extremely low. In the development of the mercury vapor turbine by the General Electric Co., Nerad and his associates1 discovered that the addition of as little as 1 ppm Ti or Zr to magnesium-deoxidized mercury reduced the mass transfer of ferrous alloys by mercury to a negligible amount. Reid2 reported that titanium was detected chemically on the surface of steels contacted with this mercury alloy in amounts varying from 2.0 to 2.6 mg per sq in., the greatest amount being found in the hottest portion of the circuit. Reid stated that the titanium forms the intermetallic compound Fe2Ti by reaction with iron on the surface of the steels. This compound was presumed to be highly insoluble in mercury. More recently, El-gert and Egan3 have reported a greater than 100-fold reduction in the rate of mass transfer of a 5 pet Cr steel by liquid bismuth upon the addition of titanium (in excess of 50 ppm) and magnesium (350 ppm) in the liquid metal, during experiments performed in thermal convection loops* over the temperature differential 700° to 615° C. Also, Shep-ard and his associates&apos; have reported that the addition of titanium to liquid bismuth and Pb-Bi eutec-tic produced a marked decrease in the rates of solution of both iron and chromium from type 410 steel capsules under static conditions. This inhibiting effect increased with repeated reuse of the capsules. Tests performed in this laboratory under carefully controlled conditions have shown that the addition of zirconium and magnesium, or titanium and magnesium, to liquid bismuth or lead greatly reduces the rate of mass transfer of chromium alloy steels and carbon steels in thermal convection loops with a maximum temperature of 550°C.5-9 The present paper will review the data obtained to date at this laboratory on the behavior of iron and steels in contact with liquid bismuth alloys containing titanium or zirconium, and will attempt to explain the role of the above additives in reducing solution mass transfer. Reaction between the Zirconium or Titanium Dissolved In Liquid Bismuth and an Iron or Steel Surface Reaction between Zirconium Dissolved in Bismuth and the Surface of Pure Iron-—A small pure iron crucible (analyzed by the supplier to contain 0.8 ppm N was contacted with bismuth containing approximately 0.1 pet Mg and varying amounts of a radioactive zirconium tracer. The crucible was then inverted at the temperature of contact. The thin residual layer of adherent bismuth was dissolved in cold, concentrated nitric acid. The crucible surface and the solidified bismuth were then analyzed for radioactive zirconium. An analysis of the activity loss on the crucible surface and the weight loss of the crucible during the nitric acid treatment showed that the acid treatment removed the zirconium that had originally been dissolved in the adherent bismuth, but not any zirconium that may have reacted with the crucible surface. The crucible was then pickled in warm aqua regia to remove all surface activity, hydrogen-fired at 600°C, and recontacted with a new liquid alloy. The results of the experiments contacted 1 hr at 450°C show, Fig. 1, a Langmuir-type adsorption with an adsorption free energy of approximately 17 keal per g atom Zr.5 This deposit was estimated to contain 1 atom of zirconium for each 7 to 8 iron atoms on the crucible surface, assuming a surface roughness factor of the pickled crucibles to be five. Increasing the temperature to 520°C caused consi-

Jan 1, 1959

INTRODUCTION The preceding chapters have brought us to a point in the mineral appraisal process where the composited sample values can now be used to estimate the grade and tonnage of the total mineral deposit. There are many techniques whereby drill hole composites and/or other sample data are used to assign grade and estimates to the surrounding rock. Matheron and his students have properly called such techniques extension functions. Before embarking upon a detailed discussion of extension functions, it is necessary that we take time to consider the concept of geostatistics as advocated by George Matheron who developed the "Theory of Regionalized Variables," which he published in 1962 (Matheron, 1971). The concept of regionalized variables has important application in the techniques of mineral appraisal. The position or location of a mineral sample within a deposit can be almost as important as its value. Geostatistics, when defined as "the application of the theory of regionalized variables* to the study of mineralized volumes of rock," takes into consideration the position as well as the magnitude of the value of the sample. The principles of geostatistics, as outlined by Matheron, represent a major step forward in the mineral evaluation process, because they provide a sound theoretical and practical basis for quantifying the geological concepts of (1) area of influence of a sample, (2) the continuity or lack of continuity of mineralization within the ore body, and (3) the lateral changes in mineralization according to the trend direction of an ore body and its orthogonal components; or in other words, a measure of the anisotropy of the deposit. Royle (1971) has defined the objects of geostatistic as being: "1. To estimate the most likely value of blocks of ore, or the values of the whole deposit; and 2. to estimate the errors of such estimates. This latter is important as, in addition to providing a check on unwarranted optimism, it shows where more valuation work may be needed." Because of the great importance of these concepts in mineral evaluation, an introduction into the theory of regionalized variables, and the study of a practical approach to its application is outlined here. REGIONALIZED VARIABLES VS. RANDOM VARIABLES Classical statistics, as discussed in earlier chapters, grew out of the study and application of probability theory. Probability is concerned with the outcome of random events and therefore classical statistics is built upon the theory of random variables, i.e., the probability of independent events. The validity of most statistical inferences depends upon sample randomness being assured for unbiased results. Where independent events cannot be assumed the results of statistical inference becomes suspect. On the other hand, geostatistics is concerned with variables that have position in space as well as magnitude, hence the term regionalized variables. Mineral deposits are not the only field to which the theory of regionalized variables is applicable. Many natural phenomena that demonstrate a relationship between change in magnitude and position in space are amenable to application of geostatistical techniques. Mineral deposits vary greatly in their geosta-

Jan 1, 1980

By J. K. Elliott, P. H. Kelly

Many engineering functions such as surface metering work and laboratory compressibility check points involve the use of liquid densities of light hydrocarbon mixtures at various pressures and temperatures. However, at the present time, no simple reliable method exists for determining density variation, particularly if the composition of the liquid is unknown. Consequently, a study was undertaken to develop and present a simple and accurate method of predicting density variation of a light hydrocarbon liquid with pressure and temperature, knowing only the density of the liquid at some condition. The experimental liquid compressibility data from API Project 37 by Sage and Lacey&apos; have been considered to be accurate within 0.5 per cent and cover a wide range of pressure (14.7 to 10,000 psia), temperature (100" to 400°F) and molecular weight (up to 150). From these data, a set of liquid density curves, which relate density to pressure, temperature and molecular weight, was developed. These curves make it possible to predict density variation with pressure and temperature. Compared to extensive laboratory compressibility data on a complex, light hydrocarbon liquid, the use of the liquid density curves resulted in an average error of less than 0.5 per cent. Based on the results of this analysis, it is concluded that the set of liquid density curves developed from the data of Sage and Lacey provides an accurate and simple method for predicting the density variation of light hydrocarbon liquids when the density at some condition is known. These curves should be very helpful in many engineering calculations, particularly in the surface metering of light hydrocarbon liquids. INTRODUCTION Many situations arise in field and engineering laboratory work, such as reservoir engineering studies, check of experimentally determined laboratory data and orifice flow-meter formulas, where liquid density factors at various pressure-temperature conditions are required. Also, the need for accurate light hydrocarbon liquid information has become more important with the advent of miscible-type displacements for secondary recovery purposes in oilfield operations. Several reliable methods are available1 - "or determining the density of liquid hydrocarbons if the composition of the liquid is known. However, there is a definite lack of methods for accurately determining the variation of density when the composition of the liquid is unknown. The purpose of this study is to review the various methods for determining hydrocarbon liquid densities and to develop a simple and reliable method of determining variation in density of light hydrocarbon liquids with pressure and temperature when the compositio~n of the liquid is unknown. METHODS FOR DETERMINING DENSITY OF LIQUIDS OF KNOWN COMPOSITION Sage, Lacey and Hicks&apos; have proposed a method to predict the density of light liquid hydrocarbons by using partial molal volumes. Data are available on experimentally developed partial liquid volumes of hydrocarbons over a rather limited range of temperature, pressure and composition. The partial mold volume method has proved satisfactory for determining the density of some hydrocarbon liquids when the composition is known. Within the range covered in the Sage, Lacey and Hicks1 data, the results agree within about 3 per cent of the experimental values. Hanson mentions the limitation of this method to a composition range of approximately 10 per cent by weight of methane, which will not allow this correction to cover most low molecular weight-light hydrocarbon liquids. Standing and Katz2 studied data on light hydrocarbon-liquid systems containing methane and ethane at high temperature and pressure and have presented a method for determining liquid densities, assuming additive volumes for all components less volatile than ethane and using apparent densities for methane and ethane. The compressibility and thermal-expansion curves used by Standing are based on assumptions that compressibility of a hydrocarbon liquid at temperatures below 300°F is a function of the liquid density at 60°F and that thermal expansion of the liquid is affected little by pressure. The information required to use this technique with an example problem is furnished by Standing.&apos; Hanson eports an average error of - 0.5 per cent using the method of apparent densities in calculating liquid densities of several volatile hydrocarbon mixtures. However, as implied, the apparent density method is not applicable for liquid density calculations when the composition of the liquid is unknown. Watson- as presented a method

By Daniel R. Hull

IN 1026 Genders&apos; reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan,3 and by Phillips and Brick,2 so that no resume is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. VAPOR SEGREGATION There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table I, which represents a [ ] cylindrical billet 7 in. in diameter by 5; in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. The lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps up a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941