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By W. A. Backofen, D. Lee, F. S. Jabara

THE empirical character of plasticity analysis insures a continuing need for measurements of the yield surfaces of anisotropic materials. Recently, Wheeler and Ireland (W-I) proposed that an octahedral yield locus could be constructed on the basis of six Knoop hardness indentations. Such simplicity would have obvious appeal, if it led to consistently dependable results. In other recent work, a much more straightforward (and more tedious) method of measurement was used to establish all quadrants of the plane-stress yield loci for two substantially anisotropic titanium alloys.2,3 The same materials have since been reex-amined by the W-I method with results being reported here. A full description of the stress state under a Knoop indentor would be complex. In principle, however, this can be avoided in relating the hardness number to a plane-stress yield locus, by the expedient of superimposing the appropriate hydrostatic component on that state of stress. Six possible orientations of in-dentor on orthogonal (symmetry) planes, along (principal) coordinate directions, are illustrated in Fig. 1(0). Pictured in Fig. l(b) are normal-stress components nominally associated with indentation n: o2(H), directly proportional to the Khn in this case, together with By overlaying a hydrostatic tension, ah, that in general is equal to the stress state around the indentation is reduced to one of plane stress in the x-y plane for which the stress ratio is a The key step in the W-I yield-locus construction is to represent the Khn for any indentor orientation as a vector quantity on the octahedral plane. In the plotting, the vector is given as deviatoric stress components along the principal axes in the ratio , where represents the direction of the minor (width) diagonal and 1 that of the major (length) diagonal. There is no attempt by W-I to justify the 7/1, although it might be supposed that the value originates in the usual ratio of major to minor diagonals in a Knoop indentation of about 7/1. If that were its origin, the link to the deviatoric stress ratio would presumably be made by first taking 7/1 and then turning to the Levy-Mises equation for isotropic material: Interpreted in this way, the W-1 approach seems arbitrary and even contradictory. Yet it would still be favored by two circumstances: the deformation under a Knoop indentor approaches plane strain: when dcw/del =a; and the shape of the locus where plane strain is represented is not overly sensitive either to the exact value of dc,/dcl or to the degree of anisotropy, within a rather wide range of both variables. The second point is illustrated below, after a few additional comments on applying hardness

Jan 1, 1968

By R. S. Wagner, W. C. Ellis

A new mechanism of crystal growth involving oapor, liquid, crnd solid phases explains many observations of the effect of implurities in crystal growth from the vapor. The role of the impuuitq is to form a liquid Solution with the crystalline tnalerial to be grown from the vapor. Since the solution is n prefevred site for deposition firorti the uapor, the liquid becorrles supersaturated. Crystal growth occurs by precipitatzon from the supersaturated liquid crt tlie solid-liquid zntevfnce. A crystalline defect, such as a screw dislocation, is not essetztial for VLS (vapor -liquid-solid) growth. The concept of the VLS mechanism is discussed in detail with reference to tire controlled growth of silicon crystals using gold, platinum, palladium, nickel, silver, or copper as an implurity agent. RECENTLY a short communication' described a new concept of crystal growth from the vapor, the VLS mechanism. In this paper we present a detailed description of the process and its application to the growth of silicon crystals and we discuss its relevance to existing concepts of .'whisker" crystal growth. Crystal growth from the vapor is usually explained by a theory proposed by Frank2 and developed in detail by Burton, Cabrera, and Frank.3 In this theory a screw dislocation terminating at the growth surface provides a self-perpetuating step. Accommodation of atoms at the step is energetically favorable, and is possible of much lower supersatu-ration than required for two-dimensional nucleation. Crystals of a unique form resulting from aniso-tropic growth from the vapor are "whisker" or filamentary ones. Such crystals have a lengthwise dimension orders of magnitude larger than those of the cross section. For most filamentary crystals both the fast-growth direction and directions of lateral growth have small Miller indices. The special growth form for a whisker crystal implies that the tip surface of the crystal must be a preferred growth site. sears4 proposed that, according to the Frank theory. a whisker contains a screw dislocation emergent at the growing tip. Such an axial defect provides a preferred growth site and accounts for unidirectional growth. The hypothesis was extended by Price. Vermilyea. and Webb," still implying the presence of a dislocation at the whisker tip. They postulated that impurities arriving at the fast-growing tip face become buried while those arriving on the surface of slow-growing lateral faces accumulate and thereby hinder growth. These considerations led to a whisker morphology. There is increasing evidence that most whisker crystals grown from the vapor are dislocation-free. Webb and his coworkers6 searched for an Eshelby twist7 in zinc? cadmium, iron. copper, silver, and palladium whisker crystals. They found unequivocal evidence for an axial screw dislocation in only one element, palladium. However, not every palladium crystal examined contained a dislocation. Observations with the electron microscope have failed to show dislocations in whisker crystals of zinc, silicon.9 and one morphology of AlN.10 Since many whiskers are completely free of dislocations, an axial dislocation does not appear to be required for whisker growth of many substances. A significant advance in understanding whisker growth has been a recognition of the need for impurities. This requirement has been clearly demonstrated for copper,11 iron,13 and silicon9-1 whiskers. For silicon, detailed studies proved conclusively that certain impurities, for example, nickel or gold, are essential. Another pertinent phenomenon which has received little attention is the presence of a liquid layer or droplets on the surface of some crystals growing from the vapor. Crystals in which this has been observed include p-toluidine,14 MoO3,15 ferrites,16 and silicon carbide.'" The liquid layers or globules were considered to be metastable phases, molecular complexes, or intermediate polymers originating from condensation of the vapor phase. The possibility has been suggested that the halide being reduced is condensed at the tip18 or adsorbed on the surface11 of a growing metal whisker, for example copper. The literature on whiskers discloses illustrations of rounded terminations at the tips. These appear. for example, on crystals of A12O3,19,20 sic,21 and BeO.22 For BeO, Edwards and Happel suggested that during growth of the whisker the rounded termination consisted of molten beryllium enclosed in a solid shell of BeO. A recent paper9 on the growth of silicon whiskers contains many observations pertinent to an understanding of the mechanisnl of whisker growth. These observations are summarized as follows. 1) Silicon whiskers are dislocation-free. 2) Certain impurities are essential for whisker growth. Without such impurities the silicon deposit is in the form of a film or consists of discrete polyhedral crystals.

Jan 1, 1965

By Hiroshi Oikawa, A. G. Guy

Recent experimental evidence has shown that it is often incorrect to neglect the reactions occurring at an interface with respect to the diffusion reactions. By introducing reaction-rate constants and k for the transfer of components 1 and 2 between the a and b phases, a phenomenological description has been devised for the coupled processes of diffusion and in-terfacial reaction. An illustrative example has been analyzed with the aid of a suitable computer program. The results indicate that for kab values on the order of 10'1 cm per sec and Ð values of about 10¯10 sq cm per sec, the interfacial reactions are significant during the first 10 2 to l0 6 sec of a diffusion experiment. Among the observable effects of the interfacial reactions in this case appear to be the burying Kirkendall markers and an anomaly in the initial shifting of these markers. THE study of diffusion between two phases is especially important because of its direct connection to phase transformations. For example, the transformation of austenite to ferrite involves diffusion in the a and ý phases and also an interfacial reaction (trans formation) at the a/? interface. If ferrite and aus-tenite are the two members in a diffusion couple, the same two reactions occur during the diffusion process. The numerical values obtained for the diffusion coefficients and interfacial-reaction constants from diffusion experiments can then be employed to predict phase-transformation behavior. Refinement of the calculations of phase transformation is also suggested by the present method for treating two-phase diffusion. In the recent paper by Nolfi et al.' only the solute com ponent is considered in the interfacial reaction accompanying a phase transformation. The present analysis demonstrates that both components must be considered. It is generally recognized that reactions of some kind must occur at the interface in a two-phase diffusion couple, but usually it is assumed that the interface reaction occurs so rapidly that its effect on the overall process is unobservable because the slower diffusion process determines the kinetics of the process. However, Seith and Heumann 2 pointed out that effects of the interfacial reaction should always occur in the early stages of diffusion, and recently Eifert et al. 3 have shown that interfacial reactions influence the composition and motion of the interface in a/ß Al-Cu diffusion couples during the entire course of prolonged, high-temperature treatments. A general procedure for handling the combined processes of interfacial reaction and diffusion in a binary, two-phase system is to introduce kinetic coefficients for the interface reactions and to develop the system of equations governing the interlinked processes of diffusion and interface reaction. The resulting equations, although not amenable to solution in closed form, can be usefully manipulated by a digital computer. INTERFACIAL REACTIONS IN TWO-PHASE DIFFUSION Consider the general case of diffusion between two solid solutions, a and ß, which are adjacent phases in a binary system, Fig. 1. Two semiinfinite bars having compositions c1 and c0ß are jointed at x = 0. If concentrations are expressed in volume fraction,4

Jan 1, 1970

By H. W. Ahrenholz

Seven weeks of 1971 were devoted to a nationwide coal walkout resulting in lost production of some 70 million tons and leaving 1971 coal production at about 550 million tons. Compounding the problem, consumption of coal in 1971 by electric utilities rose by about 5% to 336 million tons. In the mean- time, numerous contracts were awarded for coal R&D including $24.8 million given by the Office of Coal Research to Bituminous Coal Research for the construction of a coal-to-gas pilot plant using the BIGAS process. Exports declined mainly due to Japan's decrease in steel production and to that country's increase in coal imports from Canada and Australia. The advances in equipment design and mining procedures made 1971 a noteworthy year. Introduction of the variable pitch I dipper, the trend toward wheeled vehicles, the greater use of scrapers in reclamation and battery-operated vehicles and oscil-mining, and the increased activity in the areas of ventilation and dust control were given widespread approval. There were also strides made in computerization, longwall mining, roof bolting, rock dusting, mine haulage and methane detection.

Jan 2, 1972

By Frank Kneeland

SAFETY FIRST is a popular motto-most mining companies have adopted it. It is probable, however, that in the majority of cases it is only a motto and gets no further than the office stationery or the bulletin board at the mine's entrance. In but few industries is there employed a greater diversity of machinery and mechanical devices than in coal mining. The list ranges all the way from mechanical stokers to wood-working machinery and undercutters. Many of these devices, particularly those employed in wood working, are extremely dangerous. In 1913, 23 per cent. of all fatalities occurring in coal mining in the U. S. were caused by machinery of some sort or other. Although the forms of accidents occurring with mining machinery are legion, they generally arise from one or more of five causes: (a) Falls from ladders, platforms, etc.; (b) coming in contact with moving machines or parts thereof; (c) electric shocks; (d) failure of some machine part; (e) mismanipulation of valves, levers, switches or other hand-operated controlling devices. The steps which may be taken to prevent accidents from the above causes are almost as numerous as the accidents themselves. There is, and can be, no panacea for all mishaps, nor for any one class of accidents. There is no mathematical or other formula that will bring immunity under any set of conditions. Common sense is the only guide. The remedy for the first-named class of accidents is simple and generally effective-namely, make the staging, ladder, platform, or other support, abundantly strong to carry any possible weight that it may be called upon to bear; provide ample railings on platforms or runways, and non-slipping feet on movable ladders.

Jan 1, 1915

By HENRY M. HOWEL

1. Introduction.-The first part of this papers treats of the causes and the restraining of piping in steel ingots; the second& considers the causes and the restraining of -segregation; and the third proposes certain precautions in engineering specifications concerning these two defects. Into their causes I have looked carefully, with the purpose of arriving at rational methods of restraining them, and at efficient ways of detecting. and measuring the harm which they cause, so as to benefit the public by reducing this harm at once effectively and with the least expense to the manufacturer, and therefore in the end with the least expense to the consumer. In Part I., I infer that the pipe is chiefly due to what I, call the virtual expansion of the outer walls of the ingot in the early part of the freezing. I find that the upper and smooth-faced part of the pipe probably forms while the interior is still molten, but that the lower, steep, and crystal-faced part probably forms in metal which is already firm. Of the five causes which may co-operate to limit the depth of the pipe, I find that three-blow-holes, sagging, and the progress of freezing from below upwards-are usually effective. I find that the pipe may be lessened by casting (1) in wide ingots,; (2) in sand molds, especially if these are pre-heated (this is rarely expedient); (3) at the tops instead of at the bottom; (4) slowly; (5) and with the large end up; (6) by the use of a sinking-head or other means of retarding the cooling of the top; (7) by permitting blow-holes to form; and (8) by liquid compression.) Most of these I consider in some detail, and in particular I dwell on the advantages of casting with the large end up, and I propose certain administrative arrangements to permit this.

Mar 1, 1907

By Arcy A., J. G. Davis, D&apos Shock

Results of a pilot operation in the Carlsbad Basin are discussed. After hydrafracing between wells, a block of potash was removed by solution techniques. The distance between frac wells was about 200 ft, the thickness of potash mineralization, 5 ft. By proper manipulation, a feed of concentrate brine was obtained. The ex-periment showed that the thin-bedded potash could be removed by the solution techniques. The details of well construction, method of operation, and removal rates are discussed. Continental Oil Co.'s laboratory research on the fundamentals of potash solution mining has been expanded by means of a series of field tests, and subjects such as well completion and hydraulic fracturing were added to the investigation. Both single-well and multi-well systems were studied in the field work. Discussion Background: The current paper discusses one field test in which potash was solution mined by a two-well system from a thin sylvinite zone. The potential economic value of solution mining evolves from (1) the use of drilled holes and solution techniques instead of excavated shafts and caverns and (2) the ability to mine both land and marine deposits through any type of overburden geology and below conventional mining depths. Recent interest has been focused on potash' and other soluble minerals, such as trona. Solution extraction minerals, such as copper and uranium, are also worthy of important consideration. In addition, many of the techniques are directly applicable to the construction of horizontal underground storage carverns in salt. There are two general approaches to potash solution mining. The first is to mine on a single-well basis, in which the same well bore is used for both injection and production. This method is slow, and the areal extent may be quite limited in other than very thick ore zones. The second, and the preferred approach, is to mine on a multi-well basis in which the solvent is circulated between wells. This technique, if applied in a manner which allows the ore zone to be mined from the bottom upward, results in nearly all the solution taking place from the cavern roof. Salt removal rates, therefore, are very much higher than from a single-well system.l Wells can be interconnected into a multi-well pattern by several means. One is to join single-well caverns in the lower part of an ore zone. Another is to use the hydraulic fracturing techniques developed in the oil fields.' We preferred the fracture approach because of its potential for creating the greatest area of salt exposure. Test Site Description: The field tests were conducted in New Mexico's Carlsbad Basin, where the potash deposits are flat and uniform over reasonable distances. Here, 12 potash zones are present in the massive Salado Salt section. The specific target was the Third Ore Zone which is about 4 ft thick at our location and about 1150 ft deep. The test pattern was designed in the shape of an equilateral triangle with a fourth well located in the center, 200 ft from each of the vertex wells. This configuration allowed the ore zone to be hydraulically fractured from the center well with good assurance that the fracture would intersect the bore of at least one outside well. Several multi-well test patterns would be available if the fracture connected all wells. Well Completion: Surface casing was set in the top of the Salado Salt at 600 ft to shut off water flows from the surface sands, and the salt section was drilled and diamond-cored to a point below the Third Ore Zone. A drilling fluid made of diesel oil with a small amount of emulsified water was used to drill and core the salt. This fluid was highly successful in preventing enlargement of the drilled hole and in promoting good core recovery. The three outside wells were completed by setting 51/2-in. casing at the base of a streak of anhydrite about 20 ft above the ore zone. Pipe was set high so that the intersection point of the fracture could be detected even if the fracture migrated above the ore zone as it progressed outward from the center well. The center well itself was completed by cementing 51/2-in. casing through the Third Ore Zone. Cement bond logs run on the center well have shown excellent bonding. Fracturing Practice: A mechanical tool was used to cut a notch through the casing and into the salt at a point about 1 ft below the ore zone in the center well. The purpose of this notch was to fix the point of fracture entry into the salt. The fracturing was done with water at injection rtaes as high as 30 bbl per min. The salt parted at 1450 psi; and it required only 5 min for the fracture to reach the well which was 200 ft to the south. It took about 5 min more to reach the other two wells. Caliper surveys were run to locate the point of fracture entry in the three outside wells. The fracture appears to have drifted downward slightly, entering the outside wells at the top of a streak of carnallite 8 or 9 ft below the ore zone. A cross section of the wells selected for the multi-well test is shown in Fig. 1. The figure includes KC1 values based on core analysis and the trace of the fracture plane between the wells.

Jan 1, 1971

By M. F. Goudge, R. V. Tomkins

Sodium sulfate is an important chemical raw material that is being used in ever increasing quantities in modem industry. It comes on the market mainly in three forms: (1) Salt cake (Na2SO4), a relatively crude form of the anhydrous salt containing up to 3 pct impurities, and comprising about three-quarters of the North American production; (2) anhydrous sodium sulfate (Na2SO4), a refined form containing less than 0.3 pct impurities; (3) Glauber's salt, the decahydrate (Na2SO4.10H2O) containing 55.9 pct water of crystallization. Competing with salt cake from natural sources is byproduct salt cake from a number of industrial operations. For instance there is Mannheim cake resulting from the manufacture of hydrochloric acid by the reaction of salt (NaCl) and sulfuric acid in Mannheim furnaces; rayon cake, a high-quality product, resulting from the process of making rayon by the viscose process; chrome cake from the processing of sodium chromate to dichromate; phenol cake from the manufacture of phenol; also byproduct sodium sulfate resulting from the conversion of lithium sulfate to lithium carbonate; from the processing of sodium tetraborate to boric acid; from converting sodium formate to formic acid; and in the manufacture of cellophane. Sodium sulfate is also obtained as a byproduct in the manufacture of isosebasic acid. In addition strong competition has resulted from imports of byproduct salt cake from the chemical industries of a number of highly industrialized European countries. However in recent years due to technological changes the output of byproduct salt cake is rapidly diminishing and the natural deposits are becoming the most important source of sodium sulfate used in North America. For instance, the production of hydrochloric acid in Mannheim plants has become obsolete and thus the greatest single source of byproduct salt cake will disappear. Also viscose rayon is meeting strong competition from nylon and other synthetic fibers and production of byproduct salt cake from this source may do little more than remain at the present level. These factors together with increasing demand for sodium sulfate point to increased production from natural sources. In 1958, 36 pct of the total United States production was derived from natural sources and in addition 97,000 short tons was imported so that over 40 pct of the total consumption was supplied by natural sources whereas in 1953 the proportion was only 24 pct. The rapid growth in production is shown in Table 1. Principal Sodium Sulfate Minerals There are many minerals in which sodium sulfate is a constituent but those of commercial importance at the present time, and consisting wholly of sodium sulfate in either the hydrous or anhydrous states, are mirabilite and thenardite. Minerals of potential importance but consisting in part of compounds other than sodium sulfate are glauberite in which sodium sulfate is combined with calcium sulfate, and blödite in which sodium sulfate is combined with magnesium sulfate. Mirabilite (Na2SO4.10H2O) the decahydrate, consists of 24.8 pct SO3, 19.3 pct Na2O, and 55.9 pct H20. It is a colorless to opaque, soft, water-soluble mineral with a slightly bitter taste. It has a hardness of less than 2 and a specific gravity of 1.48. It forms long needle-

Jan 1, 1960

By J. P. Hirth, G. M. Pound

The flux of evaporation J from {loo) , {111), and (110) planes of silver single crystals and from poly crystalline specimens was measured at 744°C under a high vacuum using a time average weight loss method. The evaporation coefficient a was computed from the measured flux and vapor pressure data through the relationship J = aPe/21rmkT. The evaporation coefficients for the close packed planes and the poly crystalline specimens were found to be about 0.4 providing tentative confirmation of the theoretical limiting law for evaporation of metal crystals, a = 73(P/Pe) + % . The (110) planes faceted to form (111) planes, resulting in a greater evaporating area and larger a . The evaporation morphology of the plane surfaces and the surfaces of spherical single crystals is described in some detail. RECENTLY a detailed theoretical analysis of the mechanism and kinetics of metal crystal evaporation was made.1'2 A mechanism for vaporization involving the recession of monatomic ledges across a metal surface was deduced, and evaporation rate equations were derived by considering the dynamics of these ledges. In most metals, the process of evaporation is one of dissociation of atoms from ledges, surface diffusion, and desorption. The gross vaporization rate is controlled by the surface diffusion and desorption rates. It was shown that the monatomic ledges, under the action of surface diffusion gradients, tend to assume a terminal velocity and spacing. Further, it was shown that crystal edges and grain boundaries are a ready source for monatomic ledges. In the case of evaporation of large, perfect crystals with clean, low-index surfaces, the kinetic treatment1 leads to a limiting law for crystal evaporation: where J is the gross flux of vaporization, a is the evaporation coefficient, Pe the equilibrium vapor pressure, m the atomic mass, k Boltzmann's constant, T the absolute temperature, and P the actual pressure of vapor over the crystal surface. Imperfections such as grain boundaries, pores, cracks, and macroscopic steps should have the effect of causing positive departures from this limiting law. Such an imperfection is a source for monatomic ledges, which, near their origin, are closely spaced and thus give rise to higher evaporation rates there. However, under many experimental conditions,' this effect should be negligible due to the relatively low concentration of imperfections. In general, a more important cause of positive departure should be screw dislocations, and the effect of these has been considered in some detai1.2,3 Monatomic ledges emanate from points where the surface is intersected by a dislocation with a screw component normal to the surface. The dynamics of ledges arising from a screw dislocation are similar to those of ledges arising from a crystal edge. There is a perturbed region near the origin where the monatomic ledges are, under certain experimental conditions, closely spaced and the

Jan 1, 1960

By R. S. Rickard, M. C. Fuerstenau

Anodic polarization curves for iron dissolution and cathodic polarization curves for copper deposition and ferric and hydrogen ion reduction were studied. These results were used to predict the relative rates of the reactions: The rates of the first two reactions were found to be first order with respect to the reacting ion, and the rale-controlling step was diffusion of the ions to the callzode surface. The rate of hydrogen ion reduction in an oxygen-free solution is dependent on the reciprocal of the square root of the hydrogen ion activity. In solutions containing oxygen, the rate of hydrogen reduction becomes dependent on the square root of the partial pressure of oxygen. At equal concentrations copper precipitation occurs about twice as fast as ferric ion reduction. In an air-saturated solution containing 0.01 M cupric ion at pH 2, the rate of hydrogen ion reduction zs about 10 times slower than that of copper precipitation. At pH values below 3, the rate of hydrogen reduction in oxygen-free solutions is very slozu. COPPER cementation has been utilized industrially for many years as a means of recovering copper from aqueous solutions. There are many different types of cementation plants, but all simply provide a means of contacting iron with relatively dilute copper solutions. In the past little or no attention has been paid to rates or mechanisms of the reactions involved. As a result, this and other studies'-3 have been undertaken recently to establish the important parameters in this system. The reactions involved in copper cementation by iron are: Since transfer of charge is involved in every case, these reactions should be considered from an electrochemical point of view. In any electrochemical system involving electrolytic conduction, passage of electrons necessitates ion transfer to the respective electrodes according to Faraday's law. The current in the system will be proportional to the rate of ion transfer, and, therefore, when the current in the galvanic cell is known, the rates of the reactions involved can be determined. Galvanostatic electrode measurements5" are applicable for these electrochemical studies, in that with this technique polarization curves (current density vs electrode potential) are established by impressing a constant current through an electrode and measuring the electrode potential. Once the current density, electrode potential, and reacting area are known for each reaction in this cementation system, the rates of the iron-consuming reactions can be determined. EXPERIMENTAL MATERIALS Several metal electrodes were used in this investigation; they are shown in Table I. Solutions were made with reagent-grade salts and conductivity water. Air, nitrogen, and oxygen were employed. All of these gases were saturated with water and degreased prior to use. EXPERIMENTAL PROCEDURE The experimental work was divided into two general areas. The first area involved galvanostatic measurements, which were used to determine the rates of reactions as a function of various parameters. The second area comprised actual cementation experiments to check the rates predicted from the electrode measurements. Galvanostatic Electrode Experiments. Polarization curves were obtained using a standard galvanostatic technique5'= with the apparatus shown in Fig. 1. The various electrode polarization experiments were run the same way except for changes in solution composition, polarity, and type of measured electrode. The general procedure involved the following steps: 1) a solution was made 0.5 M in sulfate ion and to the desired cation concentrations; this solution was placed in a constant-temperature bath and saturated with the desired gas; 2) the electrodes were cleaned and placed in the electrode holder; 3) the previously cleaned apparatus was assembled and immersed in a constant-temperature water bath (temperature controlled to ± 0.05"C); 4) the electrode was then positioned; the solutions were introduced, and the polarization meas-

Jan 1, 1969

By P. Somasundaran, D. W. Fuerstenau

Adsorption isotherms for dodecyl sulfonate on alumina were determined at 45°C and 25°C and the data was used for calculating the partial molar heat and entropy of adsorbed ions under various concentrations. Changes in OH and AS observed at certain concentrations agree with the postulate of interaction of surfactant ions to form two-dimensional aggregates at the solid-liquid interface. Values of the total OH and AS for the aggregation process calculated using the Clausius-Clapeyron equation is used to interpret the interactions of surfactant ions with each other as well as with the solvent molecules.

Jan 1, 1973

By Charles S. Barrett, Robert F. Mehl

The system cadmium-mercury has attracted much attention, chiefly because of its importance in the study of electrochemical standard cells. The constitutional diagram, as it is accepted today, is essentially that developed by Bijl l (Fig. 1), though there has been a great amount of work done on the system by other workers.2 A year ago the senior author published a paper on the crystal structure of the system, in which were described determinations of crystal structure

Jan 1, 1930

Discussion of the paper of O. P. Hood, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2607 to 2611. R. V. Norris, Wilkes-Barre, Pa.-I have had a little experience with gasoline locomotives and I want to indorse very strongly Mr. Hood's point with regard to the danger of carbon monoxide poisoning. I think .the terrible danger is not fully realized. I was foolish enough some time ago, in investigating a gasoline locomotive, to attempt to walk out of the mine entry behind it, and for several days I felt very seriously the carbon monoxide effects. The use of gasoline locomotives ought to be confined to mine entries where there is a very large amount of air. One of the grave dangers is their great convenience and the temptation to run them into chambers for just a few moments to get a car or two. GEORGE S. RICE, Pittsburgh, Pa.-Apparently one of the great dangers is in the style of the gasoline engine. When my attention was. first directed to the type of gasoline locomotives which I saw in the foreign mines-France, Belgium, and Germany, I was most favorably impressed with them, and they have given no trouble on account of fumes, so far as I could learn. Large numbers of them were being used, but all were of small capacity, and of a kind in which the speed control is by a governor of the hit-or-miss type, the engine running continuously. Their power capacity was very low, if I remember correctly it was not over 4 or 5 h.p., but they were used under favorable conditions where the grades in the mines were slight, since the entries or tunnels bad a slight grade in favor of-the load, making about the same pull for the empties against the grade as for the load with the grade. I understand the hit-or-miss valve arrangement enables a setting that will give more perfect combustion than can be insured with the valve controlled by the operating man, as in the automobile type of valve and engine used in this country. Apparently the European type of locomotive does not have the capacity to permit use under the conditions existing in this country, where most of our entries or tunnels have variable grades and long heavy trips of mine cars are used.

Jan 4, 1915

[NORTH AMERICA UNITED STATES Alabama BIRMINGHAM BURROWS, WILLIAM C. CORD, RICHARD H. COSTON, OTIS D. JR. FAIRHOPE RUFFLES, WILLIAM R. HUNTSVILLE WAGGONER, JERRY B. MOBILE PETROUTSON, PETER C. SELMA JONES, JAMES J. JR. UNIVERSITY CUDWORTH, JAMES R. JONES, WALTER B. RICHARDS, EDWARD F.]

Jan 1, 1961

By A. R. Orban, R. B. Engdahl, J. D. Hummell

The initial phase of a research program on smoke abatement from Bessemer converters is described. In work sponsored by the American Iron and Steel Institute, a 300-lb experimental Bessemer converter was assembled to simulate blowing conditions in a commercial vessel. Measurements of smoke and dust were also made in the field on a 30-ton commercial vessel. During normal blows the dust loading from the laboratory converter averaged 0.51 lb per 1000 lb of exhaust gas. This was similar to the exhaust-gas loading of a commercial vessel. The addition of hydrogen to the blast gas of the laboratory converter caused a decided decrease in smoke density. Smoke was also reduced markedly when methane or ammonia was added instead of hydrogen. The research is continuing on a bench-scale investigation of the mechanism of smoke formation in the converter process. DURING the past 2 years, on behalf of the American Iron and Steel Institute, Battelle has been conducting a research program on the control of emissions from pneumatic steelmaking processes. The objective of the research program is to discover a practical method for reducing to an unobjectionable level the emission of smoke and dust from Bessemer converters. PRELIMINARY INVESTIGATION Although conceivably some new collecting technique may be devised which would be economically practicable for cleaning Bessemer gases, no such system based on presently known principles seems feasible because of the extremely large volume of high-temperature gases involved. Hence, the research is being directed toward prevention of smoke formation at the source. A thorough review was first made of former work to determine the present status of the cleaning of converter gases. No published work was found on work done in the United States on collecting smoke or on preventing its formation in the bottom-blown, acid-Bessemer converter. In Europe, however, a number of investigations have been made on the basic-Bessemer converter. Kosmider, Neuhaus, and Kratzenstein1 conducted tests on a 20-ton converter to obtain characteristic data for dust removal and the utilization of waste heat. They concluded that because of the submicron size of the dust, special equipment would be necessary to clean the exhaust gases. Dehne2 conducted a large number of smoke-abatement experiments at Duisburg-Huckingen in a 36-ton Thomas converter discharging into a stack. A number of wet-scrubbing and dry collectors were tried unsuccessfully. A waste-heat boiler and electrostatic collector with necessary gas precleaners was felt to be the best solution for this particular plant. Meldau and Laufhutte3 determined that the particle size was all below 1 µ in the waste gas of a bottom-blown converter. Sel'kin and zadalya4 describe the use of oxygen-water mixtures injected into a molten bath in refining open-hearth steel. They claim that with use of oxygen-water mixtures the amount of dust formed was reduced between 33.3 and 20 pct of its previous level, and emission of brown smoke almost ceased. Pepperhoff and passov5 attempted unsuccessfully to find some correlation between the optical absorption of the smoke, the flame emission, and the composition of the metal in a Thomas converter in order to determine automatically the metallurgical state in the melt. In a recent U. S. Patent (NO. 2,831,762)' issued to two Austrian inventors, Kemmetmuller and Rinesch, the inventors claim a process for treating the exhaust gases from a converter. By their method the inventors claim that the exhaust gases from the converter are cooled immediately after leaving the converter to a degree that oxidation of the metal vapors and metal particles to form Fe2O3 is inhibited in the presence of surplus oxygen. Gledhill, Carnall, and sargent7 report on cleaning the gases from oxygen lancing of pig iron in the ladle. They claim the Pease-Anthony Venturi scrubber removed 99.5 + pct of the smoke, thereby reducing the concentration to 0.1 to 0.2 grain per cu ft, which resulted in a colorless stack gas after the evaporation of water. Fischer and wahlster8 developed a small basic converter and compared the metallurgical behavior of the blow with that of a large converter. Later work by Kosmider, Neuhaus, and Hardt9 on the use of steam for reduction of smoke from an oxygen-enriched converter confirmed that the cooling effect of steam is detrimental to production. From review of all of the published information on the subject, it was concluded that a practical solution to the smoke-elimination problem had not been found. Accordingly, it was deemed desirable to investigate the feasibility of preventing the initial formation of smoke in the converter.

Jan 1, 1961

T. R. HARRISON, Washington, D. C. (written discussion). *-Mr. Kowalke shows that a high resistance millivoltmeter is subject to smaller errors, due to change in resistance of the thermocouple to which it is attached, than is a low-resistance instrument. He uses as examples instruments having resistances of 30 and 2 ohms, respectively. At the Bureau of Standards, resistances above 300 ohms would be considered high and 30 ohms rather low. In the tests on calorized-iron thermocouples, a difference between the first and third calibrations of the couples serves to show changes due to the intermediate heat treatment and only under certain conditions would changes in calibrations due to changes in the wire be detected by ,a recalibration after 1 1/2 in. had been cut from the hot-junction end of the couple and the ends rewelded. The calibration of a couple depends only on the thermoelectric prop-erties of that part of the couple which lies within the region of non-uniform temperature, i.e., the temperature gradient; hence, so long as the temperature gradient falls along wires of similar thermoelectric properties no change in the electromotive force is produced by altering the metals of those parts of the circuit that are at uniform temperature. Usually at the cold-junction end of the circuit, copper leads, brass binding posts, manganin resistance coils, and various other materials form part of the circuit, but so long as all are at a uniform temperature (or if for each junction between unlike metals there is a similar opposing junction at the same temperature) no resultant thermoelectromotive force will be produced thereby. Likewise, if a length of several inches at the hot-junction end of the couple is at uniform temperature, it matters not if this section is unlike other parts of the couple, so long as there is good metallic connection and no source of e.m.f. other than thermoelectric is present. Cutting off part of the hot end of the couple within such a region of uni-form temperature would not alter the e.m.f. of the couple.

Jan 12, 1919

By AIME AIME

APPARENTLY unperturbed by any misgiving as to ill luck connected with the mystic number thirteen -for there were exactly that number of Directors on deck-the Board held two sessions on Tuesday, Feb. 21. , . Between the executive session at 5:15 p. m. and the general session at 8:30 p. m., 28 Section and Division delegates were wests of the Directors at dinner. Committee chair- " men and past officers brought the attendance to 75. Messrs. McAuliffe, Merica, Mudd and Tally had expressed their intention to be at the Directors' meeting, but each was prevented unavoidably at the last minute. At the executive session of the Board, J. V. W. Reynders was unanimously chosen to fill the unexpired term of Dr. Becket as Director: and Eugene McAuliffe in like " manner was selected to become Vice-president to fill the vacancy created hy Dr. Becket's assumption of the Presidency. Upon nomination of President Becket the following Executive Committee was appointed: Frederick M. Becket, chairman; Howard N. Eavenson, H. A. Guess, J. V. W. Reynders and William Wraith; and the Finance Committee was appointed as follows: Henry Krumb, chairman; Paul D. Merica and H. G. Moulton. Karl Eilers was reelected Treasurer and A. B. Parsons was re- elected Secretary to serve for the ensuing year, whereupon the executive session was adjourned.

Jan 1, 1933

M. G. CORSON.'-I am not going to discuss any of the papers presented but merely the question of season cracking of brass in general. Alpha brass has been known for nearly 500 yr. and from the very beginning a number of articles were made from sheets of this alloy by the process of spinning. Metal turning lathes were not yet known but wood turning lathes already existed and the wood turners used to make the mandrils and do the brass spinning themselves. Cases of season cracking were known even then. In 1915 I was connected with a small company doing a certain amount of brass spinning. Before the war its products never gave cause for complaint but their war-time products were cracking too frequently. The reason was, that due to the exigencies of war an excessive speed-up was attempted and the material simply could not take it. Today corrosion cracking of brass is most important in the case of cartridges for small arms ammunition and shell cases for large guns. The cracking takes place in storage and too frequently it is explained by the hypothetical presence of vapors of ammonia. However, I had the experience of purchasing some 20,000 rounds for the old Vetterli rifle from the Swiss government in 1905. The rifle and the cartridges were obsolete for many years and those which I bought were stored for at least 10 yr. None of them was found to be cracked or to crack in use. And the reason again was in the amount of work used in manufacturing the cartridges between anneals. The machinery today is more powerful and the amount of

Jan 1, 1945

By N. W. Ratliff, P. J. Closmann

Production of oil by expansion from a cylindrical reservoir composed of two concentric regions of different properties has been determined as a function of time for a reservoir producing at constant terminal pressure. The parameters involved are permeability, porosity, compressibility and oil viscosity. Results agree with those of a generally accepted method for uniform reservoirs when all parameters are taken as uniform. Cumulative production at any given time is reduced below that of the uniform reservoir when a region of considerably lower permeability adjoins the well; cumulative production increases when a high-permeability region adjoins the well. Curves are presented illustrating quantitative effects of these variations. INTRODUCTION Most petroleum reservoirs can be exploited by release of pressure and consequent expansion of underground fluid. During part of the production history of certain reservoirs by this mechanism, fluid compressibility can be considered small and constant. Cumulative fluid produced by this means as a function of time was calculated for a uniform reservoir by van Everdingen and Hurst.l For certain cases where a production well has been damaged or where an acid treatment has been used, a zone of properties different from those of the reservoir may be created around the production well. In such a case, expansion of the reservoir fluid takes place in a system composed of two concentric cylindrica1 regions of different reservoir properties. Such composite systems were studied in connection with heat flow by Jaeger2 who presented a solution for temperature distribution in a radial system with an infinitely large outer radius. Similar heat flow problems have been studied by other authors Oil production from composite reservoirs was studied for constant production rate by Hurst,4 Loucks and Guerrero,5 and Carter.6 THEORY This work considers constant terminal pressure. Cumulative flow is calculated for a composite bounded system in which no flow takes place across the outer boundary (Fig. 1). Since the flow is considered to be purely radial, the problem involves only one space dimension and time. It is convenient to define the following dimen-sionless pressure drops (Fig. 1).

By AIME AIME

NAPOLEON'S dictum that an Army travels on its stomach has not changed in this present war, but the things an Army's stomach calls for would be more than strange to Napoleon. Today one of the main articles of diet for the mechanized army is oil and gasoline, and the chief and most efficient source of 'apply overland is the pipe line. It was a flexible 4-in. pipe line that supplied the voracious appetite of tanks, trucks, jeeps, and planes across the North African desert. and it is the 1800-mile pipe line from Calcutta to Kunming, Yunnan Province in China, the longest in the world, that supplied oil and 100-octane gas for the trucks, tanks, Jeeps, and planes fighting on the Assam-Burma-China front in recent months. Completion of this approximately 1800-mile pipe line to China over rivers that had never been bridged, over hill that towered 9000 ft., and over swamps

Jan 1, 1945