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By A. G. Guy

IN the course of a research on steady-state diffusion it became necessary to make diffusion calculations for a finite solid. This problem was found to be sufficiently different from the corresponding problem for the semi-infinite solid for an entirely new approach to be necessary in obtaining a useful solution. The assumption of an exponential variation of the diffusion coefficient with concentration' was no longer a practical necessity, so that the new solution offered the possibility of handling diffusion in semi-infinite solids for arbitrary variations of the diffusion coefficient with concentration. In discussing the principle on which this method of calculation is based, it is convenient to consider the relatively simple problem of one dimensional diffusion into a matrix that initially contains none of the diffusing substance. The solution of the set- ond Fick Law,?C/?t=D0?2C/?x2, for diffusion into a semi-infinite solid is3 C/C=1-F(x/2vD0t [1] where C is the concentration of the diffusing substance at a depth x cm below the surface after dif- A. G. GUY, Member AIME, and M. GOLOMB are Professor of Metollurgicol Engineering and Professor of Mathematics, respectively, Purdue University, Lafayette, Ind., A. S. YUE, formerly with Purdue University, is now with the Research Laboratory, Dow Chemical Co., Midland, Mich. TP 4505E. Manuscript, July 18,1956. fusion has occurred for t seconds; C, is the concentration of the diffusing substance at the surface of the matrix; Do is the diffusion constant, expressed in sq cm per sec; and + represents the Gauss error function. The corresponding solution for diffusion into a finite solid of thickness, 1, is conveniently written for the change in concentration, C+, at a point midway through the matrix and for times, t, great enough for the following equation to be used4 c1/2/C1=(1/2-2/?e-?2D0t/l2) [2] In Eqs. 1 and 2 the diffusion coefficient is represented by the symbol Do (rather than by D) to emphasize that these equations are valid only for constant values of D. To understand how these equations can be modified to take account of actual variations of D, such as that shown in Fig. 1, first consider the fact that for a given time of diffusion theconcentration at a given point is determined, not by the D value alone, but by the ratio x/vD0 in Eq. 1 and by a similar ratio, l2/D0 in Eq. 2. Even though in fact D varies, it is possible to keep this ratio constant by using a special coordinate system, x,, that varies with D in the appropriate manner. The necessary character of this special coordinate system can be easily visualized by imagining that

Jan 1, 1958

By C. J. Osborn

The temperature dependence of the free energies of formation of metallurgically important oxides, sulphides, chlorides, carbonates and sulphates is presented graphically, whereby the task of deriving practical metallurgical information is greatly simplified. The diagrams have been revised according to the latest available thermodynamic data. WHILE it is true that much careful investiga-tional work remains to be done, there are already available in the literature sufficient thermo-dynamic data to enable the metallurgist to predict with reasonable confidence the equilibrium conditions to be expected in most important, and potentially important, metallurgical reactions. In this connection, the careful, critical compilations of K. K. Kelley and his collaborators in numerous U. S. Bureau of Mines Bulletins are particularly valuable. However, the translation of reliable thermo-dynamic data into metallurgical language unfortunately involves lengthy manipulations of the cumbersome formulas which can be set up from heat of formation, entropy, and heat capacity data. Many years ago, Kelley20 predicted that thermo-dynamic calculations would be made in the future "with the aid of free energy, heat content, and entropy tables, rather than by means of the algebraic methods employed at present", and where such tables are available they greatly simplify the task of deriving practical metallurgical information. However, in addition to these tables, there are also available one or two reliable graphical presentations, particularly of free energy data, which may be used in the same way as the tables, but which have the added advantages that interpolation is never necessary, and that the behavior of different metals or compounds may be compared at a glance. Some years ago Professor Robert Lepsoe, Head of the Department of Metallurgy at Norways Institute of Technology (N.T.H.), began a compilation of curves showing the temperature dependence of the heat contents of the elements, and the heat contents and heats and free energies of formation of the common metallurgical compounds. With such a compilation, the thermal and free energy requirements of a reaction may be read from curves in a matter of seconds; and this statement applies not only to the formation of compounds from their elements, and to the reverse dissociation, but to any reaction involving substances whose thermodynamic properties are available. This follows from the fact that heats and free energies of formation are completely additive. For example, the free energy change associated with the chlorination of a metallic oxide at any temperature, T, is given by the free energy of formation of the chloride at temperature T minus that of the oxide also at T; both of these quantities may be read directly from curves of the type suggested above. Since this early, unpublished work of Lepsoe, both Ellingham7 and Richardson and Jeffes46 have

Jan 1, 1951

By H. l. Burghoff, C. H. Mathewson

THE study of the creep of metals under conditions of prolonged loading has received the attention of many investigators for several years and almost innumerable papers have been published on the various aspects of the subject. As it appeared that much could still be learned from a study of single crystals, the present work was carried out to study the effects of temperature and conditions of loading upon the properties and deformation in tension of single crystals of alpha brass containing about 70 per cent copper and 30 per cent zinc. In particular, it was hoped to obtain information from tests below and above the recrystallization temperature of the material, so that properties such as elastic limit, yield point or critical stress, and manner of deformation might be compared for tensile tests at an ordinary loading rate and for prolonged. loading. Accordingly, short-time tensile tests and creep tests were made at room temperature, 300º, 500° and 700°F. The two latter temperatures are above the lowest possible recrystallization temperature of polycrystalline 70-30 brass. PREVIOUS WORK Clarke and White1 have made creep tests of some copper-zinc alloys, including 70-30 brass, and copper-zinc-tin alloys at temperatures both below and above the recrystallization temperature of the materials considered. Hanson and Wheeler have studied the flow and fracture of single crystals of aluminum for short-time and prolonged tensile loading over a range of temperature extending from room temperature to 400°F., their experiments being made without consideration of the orientations of the test specimens. Extensive creep and fracture tests on single crystals of lead at room temperature have been made by Betty3 and by Baker, Betty & Moore.4 Results of the last-named investigation were published while the present work was in progress. Millers examined the elastic limit of zinc single crystals at and above room temperature by means of creep tests, while Miller and Milligan6 reported the results of tests designed to show the influence of temperature on elastic limit of single crystals of aluminum, silver and zinc. The behavior, of iron crystals under static tensile loading at room temperature was reported by Gensamer and Mehl7 while the present investigation was in progress. Their specimens exhibited a well-defined yield point, below which no appreciable creep could be detected. The manner of yielding proved interesting, as the shape of the creep-time curve for the iron crystals differed from the common type of creep curves. Elongation did not begin immediately, or at least was initially very slow. The rate of elongation then increased continuously and finally decreased to zero. This S-shaped type of elongation-time

Jan 1, 1941

By C. E. Sims, H. M. Banta, S. L. Hoyt

OVER the past few years, metallic arc welding has been extended to steels of the hardenable type. As compared with other methods of fabrication, production has been facilitated, service performance frequently has been improved, and the overall results have been so favorable that engineers and production men have placed great emphasis on this application of welding. The metallurgist and welding engineer, however, have been confronted with new problems, since, for one reason, the harder steels are more apt to crack and special precautions must be taken if sound joints are to be procured. Some of the factors that are pertinent to this problem are metallurgical, and it is an object of this contribution to discuss steel manufacture and processing methods and to show how their control assists in reducing the hazard of cracking. By this time, the problem of cracking specifically underbead cracking, or "hard cracks," or parent-metal cracks-is well known, and a large amount of work has been published, both here and abroad, dealing with this subject.1 The tests described are made under restraint to facilitate cracking and, are so designed that a semiquantitative, or at least a relative, value of the cracking tendency is obtained. As one would expect, it has been reported that the incidence of cracking increases with the carbon and alloy content of the steel. More specifically, the cracking tendency is said to increase with the hardenability of the steel, though it is now recognized that the situation is not so simple. The phenomenon itself, on the other hand, has been but loosely described, and it is in only broad generalizations that this cracking has been related to steel metallurgy. Thus, while it has been abundantly demonstrated that the hardenable aircraft steel, S.A.E. 4130, must tend to crack when arc-welded, the problem still remains of why two lots of the same composition and the same hardenability can vary so greatly in cracking tendency, or what it is about the prior metallurgical history that so strongly affects the results. Further, while the efficacy of preheating and postheating in preventing cracking is recognized and utilized in production, the mechanism by which they function seems not to have been described. These points are thought to be significant in the production of steel for fabrication by metallic arc welding and, hence, of interest to mill and process metallurgists and welding engineers. Consequently, it is another object of this paper to discuss the mechanism of parent-metal cracking, including the influence of the condition of the steel and the control of cracking by manipulation of the time-temperature conditions during and after welding. A new method of rating the cracking. tendency is also discussed, and the results of the test are related to steel composition and structure or prior history. The work to be described was the outgrowth of work in 1940-41 at Battelle Memorial Institute 0n two projects, one

Jan 1, 1945

By Edgar Dunn

PART I.-DETERMINATION OF GASES IN SMELTER FLUES. IN 1907, upon arriving in Anaconda to take up work in the testing department of the Washoe Reduction Works, the. following problem was met at the car step, so to speak: complete and. exact analysis of gases, not only at the stack, but also in all departmental flues. Taken up to employ time not otherwise needed for regular testing department work, instructions were extremely liberal for a commercial plant, to the effect that accuracy should not be sacrificed to speed. In December, 1907, the work was temporarily transferred to the Great Falls Smelter, and some of the methods here given were there worked out. Differences in smelting operations at Great Falls and Anaconda, however, necessitated further investigations and the development of a new method for S03 determinations at the latter plant, where work was resumed in July, 1908, and completed about a year later. At the time of inception of the work, data (not only on percentages, but even on methods) were found to be meager in the extreme, for one or the other of two reasons: either entire lack of experiment at a large proportion of smelters, or disinclination on the part of the managements to divulge data of any description pertaining to either results or methods. In making determinations of gaseous constituents of flues, two methods are open to consideration: 1, the drawing out of a sample, and collection of the same as a whole, to be removed to the laboratory for later analysis; and 2, the absorption in situ on the flue of one certain constituent, disregarding others for the time being, or perhaps combining two or three in one determination. The first is generally the more rapid, but it is also the more inaccurate, method of analysis, even with special type absorption apparatus, being the more largely subject to error, both of reading, and also because of leakage during complicated manipulation in the laboratory. The amount used for analysis must also, because of limit of container, be small for the first method, and an average gas is very seldom obtained, necessitating for a fair average result a large number of determinations. Consequently, when we balance the time spent in a dozen determinations of short-time samples as against the time employed in making two or three long-time determinations of various constituents in situ, we are not so certain in our statement as to the relative speed of the two methods. Moreover, the method of analysis in the laboratory of 100 cc. of flue gas is satisfactory only when constituents thus determined are present in considerable quantity, results being simply approximate when determining such compounds as sulphur dioxide, sulphur trioxide, carbon monoxide and dioxide, and arsenic trioxide and water vapor, none of which are carried in all smelter flues in amounts in excess of (or even approaching) 1 per cent by volume. Special condi-

Jan 8, 1913

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By R. J. Hafsten, E. S. Davenport, R. A. Grange

THE influence of austenite grain size upon the hardenability of steel is now fairly well understood; for a given austenite, increasing the grain size increases the depth of hardening, and, since the latter is related to the fundamental transformation behavior of austenite, it follows that austenite decomposition must, in general, be retarded by increasing grain size. To date, very little quantitative information bearing directly on the effect of austenite grain size upon the progress and result of isothermal transformation has been published. Davenport and Bain,1 and Zimmerman, Aborn and Bain2 have shown that the transformation is definitely retarded in hypereutectoid plain carbon steels at temperatures near and above the upper region of rapid transformation (Ar') when the austenite grains are increased in size. More recently, Griffiths, Pfeil and Allen3 investigated the effect of a series of different heating (austenitizing) temperatures upon the progress of isothermal transformation at 1245°F. (675°C.) and 745°F. (395°C.) in a medium carbon, low-alloy steel; while they reported no measurements of the austenite grain size, their results suggest that increase in grain size retards austenite transformation at 1245°F. (675°C.), but has no appreciable effect at 745°F (395°C.). The present paper deals with the results of a study of the isothermal transformation of austenite in a single commercial alloy steel in which a fine-grained or a coarse-grained state was induced by appropriate selection of austenitizing temperature. The data are presented in the form of isothermal transformation diagrams, which clearly show that coarsening the grains lessens the rate of transformation of austenite to proeutectoid ferrite and pearlite-that is, at temperature levels above about 1000°F. (540°C.)-but is without significant effect at lower temperatures where the transformation product is bainite or martensite. It is to be presumed that the foregoing statement would be valid, at least in principle, for many other grades of steel; it confirms again that the mechanism of transformation to a pearlitic structure is fundamentally different from that to an acicular structure. A number of related observations were made, which seem to throw some light on the transformation process as it takes place in alloy steels, particularly at temperature levels in the vicinity of 1000°F. (540°C.), where the transition from lamellar to acicular structures occurs. These data are discussed briefly in the belief that they may lead to a clearer understanding of this aspect of the subject. MATERIAL AND EXPERIMENTAL PROCEDURE The material investigated was a commercial grade of S.A.E. 4140 steel, the composition of which was as follows: 0.37 per cent C, 0.77 per cent Mn, 0.98 per cent Cr and 0.21 per cent M0. It was hot-rolled to a 1 1/8-in. round bar and normalized by air-cooling from 1800°F. (980°C.).

Jan 1, 1941

By Roshan B. Bhappu, Ronald J. Roman, Dexter H. Reynolds

The reaction between manganese dioxide and molybdenite in a water- sulfuric acid medium was studied at atmospheric pressure and from 25° to 103°C. Both solids are dissolved to give, as final products in solution, Mo(VI), S(VI), and Mn(II). Stoichiornetric relationshifis are most simply represented by the equation MoSz + YMnO2 + 15H+ - HMoO-4 + 2HSO-4 + 9Mn++ + 6H20 The rate of this reaction was found to be dependent on temperature, manganese sulfate concentration, acid concentration, and, in a complex way, the surface areas of both manganese dioxide and molybdenite. Both the total amount of manganese dioxide and tnolybdenite and the ratio of manganese dioxide to molybdenite played a part in determining the over-all rate of the reaction. The effect of acid concentration on the rate was also dependent on the ratio of manganese dioxide to molybdenite. SEVERAL reports in the literature describe reactions using manganese dioxide in water-sulfuric acid media as an oxidizing agent. Nearly all previous work describes interactions between an ion and manganese dioxide, such as the oxidation of ferrous to ferric iron,' or the interaction between a molecule in solution and manganese dioxide, such as the oxidation of toluene to benzaldehyde.2 Only a few references describe the use of solid manganese dioxide to oxidize another solid in sulfuric acid. One report3 states, "Manganese dioxide in dilute sulfuric acid solutions had no beneficial effect (in leaching copper from chalcopyrite), but in more concentrated acid solutions the rate of solution was about the same as that for permanganate." In 1902 a German patent4 described a process which used manganese dioxide in strong (50°Be') sulfuric acid for oxidizing chromite ores to soluble iron and chromium salts. The process consisted of mixing the sulfuric acid with the finely ground ore and manganese dioxide. The pulp was then heated to about 120°C and an electric current passed through it. The manganese dioxide apparently dissolved in the strong, hot acid solution, oxidized the iron and chromium and itself was reduced to manganese 11! then was oxidized at the anode back to manganese dioxide, and the cycle repeated. An extensive study5 of the kinetics of the oxidation of pyrite with manganese dioxide indicated that in dilute sulfuric acid solutions (about 0.1 N) and at elevated pressures the dissolution of the pyrite was brought about by air oxidation of the iron to ferrous sulfate, followed by manganese dioxide oxidation of the ferrous sulfate to ferric sulfate. The mechanism proposed by the authors involved the oxidation of the iron at the surface of the manganese dioxide. Also! the oxidation of sulfide sulfur to sulfate was credited to the oxygen in the air, not to the manganese dioxide. Since the metallurgical literature is lacking in information concerning the use of one solid to oxidize another solid. the current investigation was under-

Jan 1, 1965

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By Stephen Royce

[Stephen Royce.. I .......................... E. S. Moore.. 9 .......................... E. L. Bruce.. 10 ......................... J. E. Hawley.. 11 ........................ L. M. Scofield.. I 2] STEPHEN ROYCE, * Crystal Falls, Mich.Having examined and reported upon the Steep Rock Lake property and vicinity on several occasions for clients, and having kept in touch with the operation from 1938 on, the writer offers the following discussion of the valuable paper by Messrs. Roberts and Bartley, which was so kindly prepared in response to the writer's earnest request, made as a member of the Committee on Mining Geology. ORIGIN OF THE ORES The writer wishes to express complete agreement with the authors that the origin of these deposits was replacement action by hot ascending sulphide solutions of igneous origin, gaining access via the limestone and dolomite breccia channels, and acting mainly to replace the dolomite and limestone breccia with hematite and hydrated hematite. Some replacement in adjoining greenstones and tuffs by the same solutions may also have taken place, but the latter occurrences may represent replaced iron formations originally bedded in with the volcanics. Iron formation in the same relationship to volcanics is extensively developed on the western Menominee Range of Michigan, in the Middle Huronian belts; also appears in similar relations on the Vermilion Range; and is abundantly exposed in the same stratigraphic position no farther away than the southeast arm of Steep Rock Lake itself. Furthermore, the writer's classification of drill cores, made June 11, 1938, on the prop¬erty, contains the following, for hole 8, in the original strike of the A ore body: "332-342 ore; 342-350 much-leached sugary chert with thin ferruginous slate bands." This is a typical iron formation. The ore in this first group of holes (Numbers 6 to 13, incl.) is described in the writer's 1938 notes as follows: "The ore is hard, massive hematite with some limonite, and shot through with many small vugs." The breccia forms in the float ore and in the drill samples were also noted. As a field classification this does not check badly with Professor Schwartz's microscopic work. Notes supplied by Mr. Neeland, then geologist at the exploration, show: "Hole 23 has some iron formation, not logged yet." It appears therefore that there is some iron formation at the exploration, much iron formation in similar stratigraphic position in the vicinity, and iron formation similarly located as to volcanics on the Vermilion and western Menominee Ranges. Certain of the holes, notably Holes 25 and 27, showed some specular hematites resembling those known to be formed from cherty iron formation elsewhere. Hence the writer concludes that at least a small part of the Steep Rock ores results from replacement of iron formation. By far the greater part of it is, as the authors say, clearly a replaced limestone and dolomite breccia, with the breccia outlines still preserved in much of the ore, and all of the replacement is by hot ascending waters. The authors' citation of the neighboring Atikokan pyrite, pyrrhotite and magnetite

Jan 1, 1943

By Edward A. Loria

Vanadium is one of the materials being considered for use in fast-breeder nuclear reactors. It is a good heat conductor and nearly transparent to radiation, properties regarded as ideal for nuclear fuel containers. The problem has been the metal lacks ductility needed for forming. In our program at Reno Laboratory the effects of the U.S. Bureau of Mines (previous affiliation) the effects of oxygen, nitrogen, and carbon have been reported21,22 nd most recently the effects of boron and boron with carbon.23 The continuing study by the Ames Laboratory of the effects of hydrogen, the most subtle and fugitive element in its relationship to structure and properties, is commendable. The solubility of oxygen, nitrogen, and hydrogen in vanadium (and other bcc metals as well) is related to material purity. With the available limit on metal purity and the interaction (clustering) of hydrogen with the other interstitial and substitutional elements present in their base metal, would the authors comment on the tolerance of hydrogen in relation to oxy- gen that will avoid intergranular fracture and above what content or how seriously harmful in oxygen at various carbon levels? Understanding the true effects of hydrogen (and other interstitial impurities) in vanadium depends on knowledge of the amount present under various conditions and its distribution between various possible positions. Significant amounts of hydrogen may be in "thermo-dynamic" solution, but not as individual atoms in interstitial positions. It may be in grain boundaries, in subgrain boundaries, in vacancies, or in dislocations. Some of the hydrogen may be paired or in complexes with impurities in substitutional solid solution in vanadium. This makes the analysis of the effect of hydrogen vastly more difficult. It should not be expected that hydrogen in grain boundaries will affect slip in the same manner as hydrogen in interstitial positions, nor will the complexes react to heat treatment the same way as hydrogen in dislocations. It is gratifying that the authors have quoted results from two of our inestiations,' but neglected one2' which applied the Petch theory to electrorefined vanadium of high purity and analyzed the effects of oxygen, nitrogen, and carbon on the ai and ky values obtained by the extrapolation and grain size methods. Details can be found in the paper. Briefly, we obtained a ui value of 10,300 psi (t = 5150 psi) at 273°K. The metal also exhibited profuse twinning with high ductility at 123" and 77°K. Nitrogen was more effective than oxygen in increasing ui, the increase being about twice as much for the same impurity level. Carbon additions resulted in only minimal changes in Ui. The corresponding ky increased as oxygen and nitrogen increased, with nitrogen being more effective. Carbon additions resulted in little change. Although the difference in yield strength of vanadium was explained on the basis of the Cottrell-Bilby model of the tearing away of dislocations from the impurity atoms,

Jan 1, 1970

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to 1706°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous days burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the day, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By J. Peperakis

Coal mine bumps are normally associated with pillar mining under moderate or deep cover. Severe bumps at Sunnyside, however, have not been confined to pillar lines. Many have occurred in virgin development and in localities a long way from active pillar workings. As early as 1918 bumps in virgin territory were attributed to the faulted structure in the Sunnyside area.' Sunnyside is an old property, mined for more than 60 years. Both man-made and natural conditions contribute greatly to bump occurrences, and loss of life and great destruction of workings have resulted from some unusual bumps in recent years. Before Kaiser Steel acquired the Sunnyside Mines in 1950, about 21 million tons of coal had been extracted. Large areas had been worked out and equally large areas first-mined. As demand for coking coal gradually diminished, extensive blocks were shut down, and during the low production period of the 1930's mining on a very limited scale was confined to a section of the property close to the coal tipple. Following purchase of the property Kaiser Steel developed the mines into a fully modernized operation. The worked out and first mined areas covered about four square miles extending five miles along the strike and up to one and a half miles down dip from the outcrop. The sections with favorable mining conditions and clean coal had been largely extracted under the selective mining system imposed by economic conditions and the lack of cleaning plant facilities. Large reserves remained on the fringes of the worked out sections and in areas under deep cover and difficult roof. There were also considerable reserves in first-mined areas. In recent years much of Sunnyside's daily output of 7000 to 8000 tons has been derived from the partially mined localities. Many bumps have occurred when pillars have been pulled within the first-mined areas and on the fringes. The bumps have been associated with retreating pillar lines backing up against old workings and pillar lines in old first-mined areas backing up against highly stressed oversized barrier pillars surrounded by smaller pillars. In some parts of the property the upper Sunnyside seam was extensively worked in the past, and sizable areas of old works overlie the present lower seam workings. Abutment pressures from barrier pillars and pillar remnants are transmitted to the lower seam, contributing to bumps and squeeze conditions. Cover: The terrain is exceedingly rough, and cover varies considerably over relatively short horizontal distances. For example, at No. 1 mine the 2000-ft cover line is ony 2700 ft from the coal outcrop, and at No. 2 mine the cover over the main hoisting slope increases from 1000 to 2000 ft in a horizontal span of 1200 ft. Cover over the present mining sections ranges from several hundred feet in the valleys to 2500 ft under the crest of the divides. A short distance ahead of Sunnyside's deepest development down dip the cover reaches 3000 ft or more.

Jan 1, 1959

By E. S. Machlin, C. W. Chen

THIS investigation is concerned with the origin of the intercrystalline voids and cracks formed in metals and alloys subjected to stress at elevated temperature. There have been many suggestions in the recent literature relating to this problem. Greenwood' suggested that the voids may be produced by vacancy condensation. Zener has stated that shear-stress relaxation across grain boundaries could initiate high tensile stresses at the regions blocking grain boundary slip and thereby cause the formation of cracks. Chang and Grant3 have described the formation of cracks at grain boundary triple points and have experimentally verified Zener's mechanism for the grain boundary regions in the vicinity of a triple point. Subsequent to the completion of this investigation, Gifkins4 developed a model which made use of Stroh's5 mechanism of fracturing to produce sub-microscopic fractures that subsequently grow by grain boundary slip. Chen and Machlin,6 in answer to Gifkins, described a model deduced from the present investigation, in which grain boundary slip provides both the stress to fracture at grain boundary jogs and the deformation required to separate fractured jog surfaces. The possibility of gas condensation to form intercrystalline voids and cracks is eliminated as a basic mechanism because such voids and cracks are developed in vacuum melted material containing minute amounts, if any, of gaseous impurities. In a theoretical evaluation of this problem, Machlin7 concluded that void nucleation by vacancy condensation during creep-rupture is improbable but that vacancy condensation on supercritical sized voids to produce growth is probable. This investigation was begun to evaluate the suggested mechanisms for intercrystalline fracture. In particular, in order to correlate vacancy supersaturation ratios produced in creep with those determined by Bal-luffi and Seigle8 as critical for , the nucleation of voids, specimens were obtained from the same heat of brass as used by the latter authors, through the courtesy of Dr. Seigle. The experiments conducted in this investigation fall into the following categories: 1) Brass—observation of voids produced under a variety of conditions, including creep under compression, to evaluate the mechanisms of void nucleation and growth. 2) Bicrystal experiments to check the mechanism of void nucleation deduced in this investigation. 3) Morphology of intercrystalline voids produced in a variety of metals. Each set of experiments will be described and discussed separately. Experimental Techniques A special creep-rupture test rack was constructed which made it possible to apply the stress to the specimen in a controlled atmosphere of inert gas, reducing gas, or vacuum. All the creep-rupture tests on a-brass (30 pct Zn) were conducted in nitrogen under a pressure slightly above atmospheric. Either dead weight loading or constant elongation rate loading could be applied with the load measured by means of a strain gage dynamometer. In order to obtain a coarse-grained crystal structure stable at

Jan 1, 1958

By A. W. Gauger

It is with some trepidation that I approach my subject, for I know that I shall at once incur the suspicion of the mechanical engineer, with his concern for boiler tests and efficiencies; of the mining engineer, with his mechanization problems; and of the chemical engineer with his unit processes. Nevertheless, it must be recognized that the technology of fuels, the systematic body of knowledge relating to the production, processing and utilization of mineral fuels, has grown to such proportions and involves so many widely diverse applications of fundamental science and engineering that it behooves us to stop and consider just what its status is in relation to other technologies, as well as in relation to the present and future needs of the social order. The time has come when technologists, applied scientists and engineers must consider the possible effects that their achievements may have on Society. The development of a machine to - -replace -several hundred men is a fine achievement when considered solely from the point of view of creative endeavor. But what of the men who are displaced by the machine! Does not the responsibility for the development of this machine embrace as well the consequences of obsolescence and technological unemployment resulting from such development? I believe that it does and that we must recognize this fact in our practice of engineering and tech- nology as well as in the training of future engineers and technologists. Magnitude of the Fuels Industry Fuel technology is the body of knowledge that relates to the mineral fuels. The fuels industry is by far the most important of all Our mineral industries. The chart in Fig. I, reprinted from U. S. Bureau of Mines Information Circular No. 6643, indicates the compartive values of metals, fuels and other nonmetallic minerals for the year 1929. Of the grand total of 13¼ billions of dollars in value of minerals at the mines, the mineral fuels contributed 48 per cent. Coal, with 34.4 Per cent, exceeded the value of any other single mineral. In fact, the value of the production of the Pennsylvania anthracite mines alone anand exceeds the value of the gold production of the entire world. Petroleum and natural gas in 1929 contributed 14.3 per cent and 3.3 per cent, respectively, of the total value of world mineral production. So much for the world picture; let us now look at the situation in the United States. Over the 60-year period 1880 to '939, $46,409,727,000 of metal1ic products, $80,788,852,000 of fuels (coal, petroleum, natural gas, natural gasoline) and $27,871,-ooo,ooo of nonmetallic minerals other than fuels were produced. The mineral fuels have contributed 52.7 per cent of the entire mineral wealth produced over this period that has seen such tremendous industrial development in our Our As a matter of fact, our present industrial civilization has been made possible through the use of the

Jan 1, 1942

By A. W. Gauger

It is with some trepidation that I approach my subject, for I know that I shall at once incur the suspicion of the mechanical engineer, with his concern for boiler tests and efficiencies; of the mining engineer, with his mechanization problems; and of the chemical engineer with his unit processes. Nevertheless, it must be recognized that the technology of fuels, the systematic body of knowledge relating to the production, processing and utilization of mineral fuels, has grown to such proportions and involves so many widely diverse applications of fundamental science and engineering that it behooves us to stop and consider just what its status is in relation to other technologies, as well as in relation to the present and future needs of the social order. The time has come when technologists, applied scientists and engineers must consider the possible effects that their achievements may have on Society. The development of a machine to - -replace -several hundred men is a fine achievement when considered solely from the point of view of creative endeavor. But what of the men who are displaced by the machine! Does not the responsibility for the development of this machine embrace as well the consequences of obsolescence and technological unemployment resulting from such development? I believe that it does and that we must recognize this fact in our practice of engineering and tech- nology as well as in the training of future engineers and technologists. Magnitude of the Fuels Industry Fuel technology is the body of knowledge that relates to the mineral fuels. The fuels industry is by far the most important of all Our mineral industries. The chart in Fig. I, reprinted from U. S. Bureau of Mines Information Circular No. 6643, indicates the compartive values of metals, fuels and other nonmetallic minerals for the year 1929. Of the grand total of 13¼ billions of dollars in value of minerals at the mines, the mineral fuels contributed 48 per cent. Coal, with 34.4 Per cent, exceeded the value of any other single mineral. In fact, the value of the production of the Pennsylvania anthracite mines alone anand exceeds the value of the gold production of the entire world. Petroleum and natural gas in 1929 contributed 14.3 per cent and 3.3 per cent, respectively, of the total value of world mineral production. So much for the world picture; let us now look at the situation in the United States. Over the 60-year period 1880 to '939, $46,409,727,000 of metal1ic products, $80,788,852,000 of fuels (coal, petroleum, natural gas, natural gasoline) and $27,871,-ooo,ooo of nonmetallic minerals other than fuels were produced. The mineral fuels have contributed 52.7 per cent of the entire mineral wealth produced over this period that has seen such tremendous industrial development in our Our As a matter of fact, our present industrial civilization has been made possible through the use of the

Jan 1, 1942

By Irwin Roman

In studying the possibilities of a continuously recording magnetometer for use along the surface of the earth and in an airplane, the Federal Bureau of Mines was led to a study of the theoretical resolving power of magnetic observations, both in the variation of the total magnetic intensity and in each of the two cornponents ordinarily measured. Along with this general study, an attempt was made to determine the relative worth of the total intensity anomaly and the vertical anomaly in geophysical prospecting. Genera1 considerations led to three conclusions: I. In the northern magnetic hemisphere of the earth, the total intensity anomaly is offset to the south of the vertical anomaly, for a positive anomaly (see Appendix, note 1). 2. The resolving power of magnetic observations decreases rapidly with distance from the disturbing body. 3. The horizontal anomaly has little value in prediction of the disturbing body but might be useful in making a choice between bodies suggested by the vertical or total anomaly. Some of the considerations leading to these conclusions were: I. The normal intensity and the anomalous intensity are vectorially additive; hence for a positive anomaly in the northern magnetic hemisphere the total intensity will be a maximum at some point south of the disturbing body and north of the point at which the line to the disturbing body is parallel to the normal earth's field. The anomaly itself has a maximum value directly above the body. For a positive anomaly of constant magnitude, the total intensity will be a maximum when the anomaly vector is parallel to the normal vector. This is shown schematically in Fig. I (not to scale) for a magnetic distribution not restricted to a relatively thin sheet in the magnetic meridian. The normal field has a magnitude 10 with vertical component V0 and horizontal component Ho. Six station points along a traverse across the body from south to north are shown at M to S. At each of these stations the normal magnetic field vector terminates at F. At each of these stations the magnetic field vector due to the disturbing body B terminates at A. The line through the station point and the point A passes through B. The magnitude of the anomaly, indicated by the length of the vector terminating at A, is proportional to some power of the distance from the station point to the disturbing body. If the disturbing body B is a concentrated point of magnetic material, the anomaly is proportional to the inverse second power of the distance. For a uniform magnetic distribution over a line perpendicular to the observed traverse, the anomaly is proportional to the inverse first power of the distance. For surface distributions, the law of intensity is more complicated. At each field point, the total magnetic intensity T is the vector sum of the

Jan 1, 1949

By Howard A. Meyerhoff

In western Argentina, in the Province of Mendoza and the Territory of Neuquen, there is a series of solid bitumen deposits which are claimed to be the most extensive in the world. In a linear belt 500 km (311 miles) long, roughly paralleling the axis of the Andes but occupying a variety of positions with respect to the orogenic structures, more than 100 outcrops have been reported. Approximately 70 of these have been prospected, and some mining has been planned or attempted for about half this number. Limited tonnage, high sulphur content, inaccessibility, labor shortages, and disastrous fires have taken a heavy toll among these operations, and in 1947, only 4 deposits were being actively mined, but 8 more were being explored and developed with a view to placing them in production. Inasmuch as these deposits are currently yielding a substantial fraction of Argentina's limited domestic supply of solid fuels, a brief account of the deposits and of the small industry based upon them will provide a commentary on Argentina's fuel problem. Character of Solid Bitumens The solid bitumens of Mendoza and Neuquen are petroleum derivatives, as is indicated by the following ultimate analysis : Constituents Per Cent Hydrogen.................... 6.8 Carbon...................... 82.4 Nitrogen..................... 1.6 Oxygen...................... 2.7 Sulphur...................... 2.2 Ash.......................... 4.3 100. 0 In physical appearance they bear a close resemblance to coal and are commonly called carbon. Their specific gravity has an extreme range of 1.10 to 1.777 in 36 samples weighed, but the average is between 1.14 and 1.24. The material is black, lustrous to dull, with blocky to sub-con-choidal fracture. Though brittle, the purest material is softer than anthracite and exhibits slightly more cohesion. This bituminous material is generally known as asfaltita or asphaltite, but definitive chemical studies indicate that the term asphaltite or grahamite can be applied correctly only to the exceptionally pure material of the Auca Mahuida district in Neuquen. Some other name should be used for the chemically variable bitumens found in all other districts, and the designation "asphaltitic pyrobitumen" has been proposed by Carlos A. S. Piscione.1 At the present time these bitumens are finding favor as solid fuel and as a gas-producing medium. They yield heat values of 8650 to 9750 cal,2 or 14,500 to 16,750 Btu per pound, and in consequence of their excellent heating qualities and the scarcity of imported coal, they are marketed as far away as Buenos Aires at a price of go to 95 pesos, or approximately $22 to 23, per metric ton. In burning, the material swells and decomposes into solid, fluid, and gaseous fractions which burn violently though nonexplosively. Its combustibility has been responsible for disasters and virtually complete destruction at Mina La Es-peranza and Mina Santa Marta, and for minor mishaps elsewhere, as at Mina Escondida in August 1947.

Jan 1, 1949