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By Cyril Wells, Robert F. Mehl

THE practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out 1,13 This importance ties chiefly, though by no means only, in the study of carburizing and in the study of reactions involved in the eutectoid inversion in steel The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in y-Fe and their mutual effects are measured with precision The present paper reports the results of meas¬urements of diffusion coefficients D of manganese in -y-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients [$] Data on the rate of diffusion of manganese in y-Fe have been reported by Fry2 and by Paschke and Hauttmann 3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq cm per sec at 960°, which will be shown to be incorrect by many orders of magnitude Paschke and Hauttmann gave a rough value of 9 6 X 10-8 sq cm per sec at 1400° Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon METHOD AND MATERIALS Method -The method employed is identical with that used earlier 5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded The diffusion anneals were performed in argon, except one (test 18) in which hydrogen was employed for purposes noted below The temperatures reported are accurate to about 3° and constant within I°C , the diffusion times are reported to the nearest half hour The specimens were furnace-cooled after the diffusion anneal at about 2° per min Layers, usually 0 004 in thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0 01 per cent Mn, the distances of these layers from the interface was measured to ±0 0002 in The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions e The D values calculated by these two methods do not differ appreciably 5 The Grube solution was used except in tests in which the effect of concentration upon D was greater than 50 per cent, in such cases the Matano method, which explicitly provides for the variation of D with concentration,1 is the more reliable In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer In 3 of the 30 tests, however, this is not justified, and the D values

Jan 1, 1941

By G. J. Saulnier, K. E. Goddard

The US Geological Survey has developed mathematical modeling techniques to assess potential impacts on the hydrologic system resulting from mining of coal and oil shale in northwestern Colorado. Potential impacts of oil shale mining on groundwater hydrology have been simulated using a quasi-three-dimensional, finite-difference model. The model has been used to simulate hypothetical mine dewatering operations at two proposed oil shale mines. Dissolved-solids distribution and solute transport were simulated with a three-dimensional, finite-difference model that was used to evaluate the effects of flooding in hypothetical abandoned mines. The potential impacts of coal and oil shale mining on water-sheds were investigated using a digital watershed model. This deterministic physical-process model predicts responses of the hydrologic system to modifications resulting from mining in basins having snow as the major source of runoff and recharge. Potential impacts of coal development on surface water quality were investigated using a river quality assessment model. The models developed by the US Geological Survey have been useful in defining the potential effects of mining in northwestern Colorado. They are an important first step in analyzing the existing data base and in predicting impacts and new data needs. The models may not be totally applicable on the local scale but are very meaningful on the regional level.

Jan 1, 1983

By C. Gatlin, N. E. Garner

Results of impulsive wedge penetration tests on two synthetic, plastically deforming rocks are presented. Basic data obtained were force-time, displacement-time, and force-displacement curves for the impacts, plus the crater geometry. Wedge geometry and blow frequency were varied over a considerable range. The synthetic rocks consisted of wax-sand mixtures; two waxes of diflerent ductilities were used to provide variable "rock" characteristics. Conventional triaxial tests showed that these synthetic rocks exhibited force-deformation curves and Mohr envelopes quite similar to real rocks, except that strengths were much lower. Measured forces from static penetration tests agreed closely with theoretical values; however, dynamic force values were much higher than the static. These latter disparities are attributed to the viscous nature of the waxes. Thus the utility of these or similar rock models must depend on the scaling of rock viscosity, which is as yet unknown for impulsive loadings at elevated stress states. It appears, however, that some macroscopic, static phenomena may be studied with wax-sand rock models. INTRODUCTION The resistance of solid materials to indentation or perforation by projectiles or other penetrators has been studied by workers in many areas. Despite these efforts no universally accepted laws or formulas are available for describing experimental observations. In the metals field the force-deformation behavior of impacting bodies is often analyzed by the Hertz law for elastic collisions, the Meyer law if plastic deformations occur, or some combination of both.' The similarities of these expressions to empirical drilling formulas of the oil industry are apparent. Beginning with the basic contributions of Simon and co-workers at Battelle,' a number of experimental papers concerning the reaction of rocks to vertical impact have appeared in the U. S. mining and petroleum literature.'-' Most published data have, to date, been obtained at atmospheric pressure, although some early high pressure information was reported by Payne and Chippendale.8 Maurer" has recently utilized available brittle impact data to develop a drilling rate equation based on the experimentally observed proportionality between crater volume and blow energy. His result agreed with earlier efforts by both Somerton, who used dimensional analysis, and Outmans, who used plasticity theory. It has long been known that rocks exhibit different modes of failure depending on the state of stress. The literature in this area is considerable; however, papers by Bredthauer, Handin and Hager,13 nd Robinson", are adequate to illustrate the point. Since rocks flow plastically at certain triaxial stress conditions, the mathematical theory of plasticity has been used to analyze the rock drilling problem. Cheatham'" has altered the wedge identation solution of Randtl to rocks, and has developed useful equations for penetrator forces under a variety of conditions. Outmans" has utilized Hill's solution in a similar manner to develop a drilling rate equation. Both Cheatham and Outmans used the linear Mohr-Coulomb rule to relate rock strength and confining pressure. The actual stress at the hole bottom is not easily ascertained, although photoelastic studies by Galle and Wil-hoit," plus the analytical treatment of Cheatham and wilhoiti8 provide some insight. Consequently it is not clear to what extent the highly idealized rheological model of a perfectly plastic solid can be realistically applied to the rock drilling problem. This paper is the first report on a long range experimental study of crater formation in rocks at elevated stress states. The data presented here are from the first phase of the project. Data obtained from impulsive wedge impacts on two synthetic, plastically deforming rocks are presented. MODEL ROCKS Geologists have long been faced with modelling the behavior of the earth and, as a consequence, have studied scaling problems in some detail.' In general, their main problem is handling the wide disparity between laboratory and geologic time. In our studies the time effects (blow velocity or rate of loading, blow duration, etc.) were essentiafly the same for both. model and prototype, as were were geometry and tooth penetration. Thus application of available scaling laws suggests that Similarity is obtained if the stress-strain curves of model and prototype are similar." For this reason Hubbert and Willis''

By T. H. Alden

T. H. Alden (General Electric Research Laboratory)—This paper as well as earlier ones of Dr. Wood represent an important contribution to the experimental description of fatigue fracture. The mechanism of fracture proposed by the authors, however, is not established by this data nor supported by other data existing in the literature. Although taper section metallography provides a rather detailed picture of fatigue crack geometry, photographs so obtained must be interpreted with care. The narrow bands revealed by etching, frequently associated with surface notches, are labeled by the authors "fissures". Measurement shows, taking into account the 20 to 1 taper magnification, that the depth of these structures is at most 2 to 3 times the width. This distinction is important in the conception of a mechanism of crack formation. It is difficult, for example, to imagine a deep, narrow fissure arising from a "ratchet slip" model. A surface notch, on the other hand, may form easily by this mechanism. The notches observed in the present work are the subsurface evidence of the surface slip bands or striations in which fatigue cracks are known to originate.4-6 It is clear that an understanding of the structure of these slip bands is of key importance in understanding the mechanism of fracture. The evidence presented shows that these regions etch preferentially, possibly because they contain a high density of lattice defects, or as the authors state equivalently, because they are "abnormally distorted." However, it is not possible to conclude that the distortion consists of a high density of vacant lattice sites. The fact of a high total shear strain in itself does not assure a predominance of point defects as opposed to other defects, for example, dislocations. Other evidence in the literature which suggests unusual densities of point defects formed by fatigue7-' refers not to the striations or fissures, but to the material between fissures (the "matrix"). If a choice must be made, the preferential etching would seem to be evidence for a high dislocation density, since dislocations are known to encourage chemical attack in copper;g no such effect is known for the case of point defects. A third alternative is that the slip bands are actually cracked, but that near its tip the crack is too narrow to be detected by the authors' metal-lographic technique. In this case the rapid etching can be readily understood in terms of the increased chemical activity of surface atoms. Unless a vacancy mechanism is operative, the motion of dislocations to-and-fro on single slip planes will not lead to crack growth. Point defect or dislocation loop generation are the principal non-reversible effects predicted by this model. In any case, the nonuniform roughening of the surface in a slip band6 requires a flexibility of dislocation motion which is not a part of the to-and-fro fine slip idea. The same is probably true of crack growth by a shear mechanism. Either some dislocations must change their slip planes near the end of the band and return on different planes,'0 or dislocations of opposite sign annihilate." The mechanism by which these processes occur in copper at room temperature or below is that of cross slip. Thus cross slip appears to be essential to fatigue crack growth.6'10"12 The fact that a tensile stress opens the slip bands into broad cracks does not indicate the structure of the bands or the mechanism by which cracks form. The charactersitic concentration of slip into bands during fatigue shows a low resistance to shear strain in these regions. (This fact in itself may be inconsistent with a high concentration of vacancies.) The authors contend also that continuing shear produces an additional mechanical weakening so that the bands fracture easily (are pulled apart) under the influence of the superimposed tensile stress. It is equally possible that the only weakness is a weakness in shear, that the crack propagates by a shear mechanism, and that subsequently the tensile stress pulls the crack apart. Even the direct observation of bands opened by a tensile stress would not be conclusive since, as argued above, they may be fine cracks. The same argument applies to internal cracks, their existence in the presence of a tensile stress not indicating the mechanism of formation. Internal cracks originating in regions of heavy shear have also been seen following tensile deformation of OFHC copper,13 so that this mode of fracture is not unique to combined tensile and fatigue straining. The authors point out in their companion report14 that 90 pct of the cracks formed during pure tor-sional strain were within 8 deg of the normal to the specimen axis. If the tensile stress were an important factor in crack propagation, it is surprising that the cracks cluster about the plane in which the normal stress vanishes. Similarly, a study of zinc single crystals showed that for various orientations the life correlated well with the resolved shear stress on the basal plane,'= and was not dependent on the normal stress across this plane. W. A. Wood and H. M. Bendler (Authors' reply) -Dr. Alden's discussion emphasizes the essential point in the relation of slip band structure to

Jan 1, 1963

By AIME AIME

METALLIC corrosion, which results from the chemical affinity of different metals for non- metallic elements, should be considered from both the kinetic and static viewpoints. From the stand- point of statics the metals may be arranged in the order of their affinity for oxygen, chlorine or any other acid- forming element. They may also be arranged in the order of the magnitude of the heat of combination of their corresponding compounds. It is misleading to talk about some metals as "noble," because these relations are all relative; and the order varies for oxygen, chlorine or whatever the element may be. A third way to arrange the metals is by their solution pressures. These three methods indicate that one metal is better under one set of conditions, but not so good under other conditions. Considering the problem from the standpoint of kinetics, the thing which saves most metals is what may be called the sluggishness of reactions. Using organic substances as an example, we know they will all oxidize, but fortunately they do so rather slowly. An increase in temperature always means an increase in the reaction rate, and preventing corrosion at high temperatures is a greater problem than at low temperatures. A second consideration is to avoid all sub- stances which might provoke catalytic action, and as it is generally impossible to foresee what substances might do this, the thing is to avoid all substances other than the main constituents of the alloys. A third consideration is to avoid local electrolytic action, which again indicates the advisability of avoiding the contact of differing substances.

Jan 1, 1926

By Harold Margalin, Elmars Ence

M. H. Mueller, M. V. Nevitt, and H. W. Knott (Argonne National Laboratory)—We have reported1 the crystal structure of Ti2CU as body centered tetragonal with a. = 2.944A and co = 10.786A, six atoms per unit cell, and space groupl4/mmm(MoSi2 type). This cell is larger but definitely related to the unit cell reported by the authors. It permits definite positions for the titanium and copper atoms in the cell located as follows: 2 Cu (a) 0 0 0; 1/2 1/2 1/2 4 Ti (e) 0 0 z; 1/2 1/2 1/2 + z; 0 0z; 1/2 1/2 1/2- z where z = 0.341 The face centered tetragonal cell reported by the authors can be transformed to a small body centered tetragonal cell with flo (small bet) = ao(fct)v2 Both unit cells have the same CO. Neither the face centered tetragonal cell with four atoms per unit cell nor the small body centered tetragonal cell with its two atoms per unit cell lend themselves conveniently to an orderly arrangment of the 2 to 1 ratio of titanium to copper atoms. When the co of this small body centered cell is tripled, however, a large body centered tetragonal cell results with six atoms per unit cell as described above. We had also noted that the X-ray patterns of Ti2Cu indicated that the structure could be approximately described by the face centered tetragonal cell as reported by the authors; how- ever, there was evidence for a few additional very weak lines whose positions indicated a larger unit cell. Since the X-ray scattering amplitudes of titanium and copper are nearly equal, it is evident that it is difficult to distinguish their positions especially from X-ray powder patterns. It was therefore decided to look at a powder pattern obtained by neutron diffraction since the scattering amplitudes of the two elements are considerably different in magnitude and opposite in sign. The sample used for neutron diffraction was selected from a group of three alloys prepared by arc melting using crystal bar titanium of 99.92 pet nominal purity and 99.999 pet pure Cu. The alloys designated as A, B, and C had the following respective compositions: Ti-32.8 at. pet Cu, Ti-33.3 at. pet Cu, and Ti-33.8 at. pet Cu. On the basis of the melting losses incurred, it was established that the actual concentration of either component in any of the alloys probably did not deviate from the intended value by as much as 0.1 at. pet. The alloys were annealed for 5 days at 700°C in evacuated Vycor capsules and quenched in tap water. The metallographic structures of these alloys are shown in Fig. 1. None of the alloys contained sufficient second phase to permit its positive identification. Since alloy B contained the least amount of second phase and since its composition placed it closest to the ideal stoichiometry, it was chosen for the neutron diffraction study. The oxygen content of alloy B was found by chemical analysis to be 0.06 at. pet. This particular intermetallic compound is especially suitable for investigation with neutron diffraction since if the titanium and copper atoms have a random statistical distribution, a near null-matrix would result in which there would be practically no coherent scattering of neutrons, and hence no Bragg diffraction peaks. Such a condition could come

Jan 1, 1962

By R. M. Howe, J. Spotts McDowell

Preparation and Use.—Magnesite is an important refractory in open-hearth, heating, and electric furnaces for steel-making and in many of those employed in the metallurgy of copper and lead. It is sold in the form of brick, finely ground "furnace magnesite" for bricklaying, and dead-burned grains for making and repairing furnace bottoms. The latter are a mixture of granules varying in size from pieces of about 5/8 in. (1.6 cm.) diameter to very fine but sandy particles. Dead-burned magnesite results from calcining the crude or lightly burned mineral at a temperaturc that will not merely drive off practically all the CO2, but will also cause sintering of the particles. During this process the pieces shrink considerably and become hard, dense, and inert to atmospheric moisture and CO2; under-burned material, on the other hand, will hydrate on exposure to the air. A small percentage of ferric oxide seems to be necessary for the production of a satisfactory sinter; from 4.5 to 8 per cent. in the dead-burned grains is considered the most desirable amount. Dolomite has been little used for brickmaking in the United States, but it is prepared for use in the granular condition calcined or "double-burned" and is the principal ingredient of several materials offered for sale under various trade names for refractory purposes. Dolomitic refractories are almost wholly confined to the open-hearth and electric furnaces, where they are used for fettling and as substitutes for magnesite. Much more magnesite and dolomite are used for basic open-hearth steel-making than for all other refractory purposes. The hearth of the furnace is usually built up of magnesite brick and dead-burned grain magnesite so laid that the brick base is protected by a working bottom of the granular material. The latter is sintered into place in layers 1/2 to 1 in: (1.25 to 2.5 cm.) thick to a total depth of 12 to 18 in. (30 to 45 cm.) at the center of the furnace. After each heat, burned dolomite is thrown against the banks as high as it will stick, and all holes in the bottom are Glled. At most plants such holes, at the end of each week, are also carefully filled with dead-burned grain magnesite. For temporary

Jan 1, 1920

By J. Spotts McDowell

Preparation and Use.-Magnesite is an important refractory in open-hearth, heating, and electric furnaces for steel-making and in many of those employed in the metallurgy of copper and lead. It is sold in the form of brick, finely ground "furnace magnesite" for brick-laying, and dead-burned grains for making and repairing furnace bottoms. The latter are a mixture of granules varying in size from pieces of about 5/8 in. (1.6 cm.) diameter to very fine but sandy particles. Dead-burned magnesite results from calcining 'the crude or lightly burned mineral at a temperature that will not merely drive off practically all the CO2, but will also cause sintering of the particles. During this process the pieces shrink considerably and become hard, dense, and inert to atmospheric moisture and C02; under-burned material, on the other hand, will hydrate on exposure to the air. A small percentage of ferric oxide seems to be necessary for the production of a satisfactory sinter; from 4.5 to 8 per cent. in the dead-burned grains is considered the most desirable amount. Dolomite has been little used for brick-making in the United States, but it is prepared for use in the granular condition calcined or "double-burned" and is the principal ingredient of several materials offered for sale under various trade names for refractory purposes. Dolomitic refractories are almost wholly confined to the open-hearth and electric furnaces, where they are used for fettling and as substitutes for magnesite. Much more magnesite and dolomite are used for basic open-hearth steel-making than for all other refractory purposes. The hearth of the furnace is usually built up of magnesite brick and dead-burned grain magnesite so laid that the brick base is protected by a working bottom of the granular material. The latter is sintered into place in layers 1 to 2 in. (2.5 to 5 cm.) thick to a total depth of 12 to 18 in. (30 to 45 cm.) at the center of the furnace. After each heat, burned dolomite is thrown against the banks as high as it will stick, and all holes in the bottom are filled. At most plants such holes, at the end of each week, are also

Jan 2, 1919

By Charles W. Bauer

Most of the aluminum produced in the United States today is derived from foreign bauxite deposits. Earth Sciences, Inc. initiated a program to evaluate domestic non bauxite sources for alumina in the 1960's. In the initial evaluation of alunite, domestic resources were not sufficient to support development. An exploration program led to the discovery of large deposits of alunite in Utah and several other western states. Identification of alunite is difficult as both its physical and chemical characteristics are similar to the minerals with which it is associated. Most of the significant alunite deposits in the western United States are replacement type deposits. These deposits have formed as a result of hydrothermal alteration of volcanic, sub-volcanic, and igneous rocks. Typical alunite deposits contain between 30 and 50% alunite and 50 and 70% quartz, with minor amounts of other minerals. Four mineralogical zones are common in these systems. They include a siliceous zone, a quartz-alunite zone, a kaolinite zone, and a chlorite-montmorillonite zone. Total US reserves of alunite were estimated at 20 Mt fat 30% alunite) by the US Bureau of Mines in 1941. More recent work by the US Geological Survey estimates reserves of 252 Mt and potential resources at 1.4 Gt. Reserves and resources estimated for 23 properties on which field work has been done by ESI are considerably higher. Most of these properties have reserves and potential resources of several hundred million metric tons. The combined demonstrated reserves of these properties are estimated to be about 650 Mt. Inferred reserves are estimated at 2.5 Gt and potential resources at 8 Gt. It appears that the US has sufficient reserves and resources for alunite to be considered as a potential nonbauxite source of alumina.

Jan 1, 1982

By T. S. Lovering

The Moffat tunnel passes through the continental divide about 50 miles west of Denver, Colo., on the Denver & Salt Lake R. R.: It is 16 ft. wide, 24 ft. high, and 32,383 ft. long, a distance of a little more than 6 miles. The advantages accruing from its construction may be briefly summarized as follows: The tunnel eliminates 27 miles of grade averaging more than 3.5 per cent. and actually running well over 4 per cent. in many places, and changes the steepest grade from 4.5 to 2 per cent. It reduced the peak of the railroad from 11,660 to 9249 ft. which enables one engine to pull four times as much freight as it could before the tunnel was built. If the Denver & Salt Lake R. R. completes its line, this road will shorten the distance between Denver and Salt Lake City by 200 miles and will have no steeper grades than the lines now connecting the two cities. The proposal to drive the tunnel through the divide dates back about 25 years and D. H. Moffat, who was the leading spirit in the organization of the Denver & Salt Lake R. R. spent much of his time and energy in efforts to raise money for the tunnel that bears his name. He was unsuccessful and died before the work was started. In 1920 an effort was made to obtain state legislation favoring a bond issue to finance three important railroad tunnels in Colorado but the measure was defeated, largely through the efforts of the citizens of the region near Pueblo. A few years later devastating floods caused the Pueblo voters to seek relief from the state and at this time they withdrew their objection to the tunnel bond issue. As a result, a $6,720,000 bond was issued to finance the Moffat tunnel. Construction bids were so high that the work was finally allotted on a scheme analogous to a cost-plus basis. The contract was awarded to Hitchcock and Tinckler, who are paid a fee of $140,000 for driving the tunnel. All bills are paid by the Moffat Tunnel Commission. The contract was let Sept. 19, 1923, and Hitchcock and Tinckler agreed to complete the work by July 19, 1927. In the event of finishing before this date they were to be given a bonus of $1000 a day and

Jan 1, 1928

By Reino Kurppa

The Pyhäsalmi mine of the Outokumpu Co. is located in central Finland (Fig. 1). The deposit was discovered in the autumn of 1958. Construction of the mine was started a year later, and production began on Mar. 1, 1962 (Fig. 2). At present, 750,000 metric tons (mt) of ore and a nearly equal amount of country rock are mined annually. Slightly over one-half million tons of various concentrates are produced per year, of which 85% is pyrite concentrate, 10% zinc concentrate, and 5% copper concentrate. The pyrite concentrate is treated in the company's pyrite smelter,1 yielding elementary sulfur, sulfur dioxide, and iron-oxide cinders, as well as electric power. Thus all the sulfides, totaling 75% of the ore, are of economic value. This is a fact which had a bearing on the development of the stoping method. GEOLOGY The ore is of breccia type containing fragments of country rock of varying sizes. It is coarse-grained pyrite ore containing sphalerite and chalcopyrite as a matrix between the pyrite grains. Only small amounts of pyrrhotite have been observed in certain marginal parts of the orebody. The ore averages 0.85% Cu, 3.0% Zn, 38% S, and 33% Fe. The orebody extends from the surface down to at least 500 m, which is the lowest level from which present information has been obtained. Horizontally, the orebody is 650 m long. It is 75 m wide at its central part, narrowing towards the ends (Fig. 3). At a depth of 115 m, the orebody suddenly narrows down to a thickness of 25 to 30 m. In the northern part of the orebody, the dip is 50° to 70°, but elsewhere it is almost vertical (Fig. 3).

Jan 1, 1969

The Editor, with the full realization of his own forgetfulness of political duties until it is brought to his attention perhaps by some unfavorable election already. consummated, wishes to remind the thinking men who compose the body of the membership of this Institute that never before in the history of the country has it been so important that we should be represented at Washington, and in our State Legislatures, by men of vision, high character, courage, broad experience in the more important affairs of life, and undoubted loyalty. Let us all endeavor to secure the nomination and election of this type of man, and let us, each in his own district (which collectively will represent practically every important locality in the Union) carefully scrutinize all candidates for election and work for the-best one who seems to have any chance of being. successful. Let its place ourselves in communication with political leaders, newspaper men of prominence, and public men generally, strengthening our own appreciation of the importance of the election at this time and cooperating for the purpose of obtaining candidates of the highest character. Upon the men of intellect depends chiefly the burden of wise selections at this time. Congressional elections will occur this Fall in the following states:

Jan 8, 1918

By E. Marburg

Most ingots complete solidification vertically rather than transversely. This conclusion is based on complete solidification patterns of big-end-up and big-end-down ingots developed from dumped and split ingots. New mechanisms for segregation in ingots are proposed. Internal soundness in ingots is found to depend upon adequate width of vertical core. A LTHOUGH it has long been recognized that the A internal soundness of ingots is principally been recognizedthatthedependent on the process of solidification, knowledge of this process is still only fragmentary. The mechanisms causing the several types of segregation in ingots, which mechanisms are necessarily related to the solidification process, are not well understood. In absence of a better conception of the solidification process, it seems hardly surprising that mold design varies widely. Guiding principles for mold design are needed. At stake in the improvement of ingot quality are not only improved properties of steel but also appreciably higher yields of sound steel, which would considerably decrease manufacturing costs. In the present study, following a general description of the several types of segregation in ingots, Fig. 1, complete solidification patterns of a big-endup and a big-end-down ingot, including the zones of accelerated solidification, have been reconstructed. In both ingots, a core of vertical solidification extends from the base cone to the hot-top junction. Based on the finding that ingots complete solidification vertically rather than transversely, as has been previously assumed, new mechanisms for segregation in ingots are proposed. Internal soundness in ingots is found to depend upon the width of the vertical core, which in turn depends principally upon the width to height (w/h) ratio of the ingot. Solidification patterns of ingots are of three general types: 1—those in which vertical solidification does not reach the top, 2—those in which vertical solidification just reaches the top of the ingot, and 3—those in which vertical solidification reaches the top some time before transverse solidification would reach the middle of the ingot, so that a vertical core of definite width at the top of the ingot is developed. Axial defects vary characteristically with the solidification pattern. Examples of ingots of each type are presented. Dumped ingot data reported by Nelson' have been used in developing families of curves of transverse and vertical solidification, and in deriving the effect of the w/h ratio upon the solidification pattern. Photographs of many ingots split at Homestead and at Duquesne Works, United States Steel CO., as well as those published by the British Iron and Steel Institute,' have been studied and analyzed. In the interest of brevity, only typical ingots of each type or classification from the above sources have been reproduced. Segregation in Ingots Segregation in ingots falls into three principal classifications: 1—lamellar segregation, as revealed in sulphur prints (Figs. 2 and 3); 2—zone segregation, or broad variations in composition; and 3— interdendritic, or microsegregation. The last class, of minor importance, is not considered here. When liquid metal cools, according to the theory of differential or selective solidification,2 metal of relatively high purity selectively solidifies first. Liquid segregates (principally carbon, phosphorus,

Jan 1, 1954

By R. W. Raymond

THE situation in 1872, from the standpoint of the prospector, the locator, the possessory claimant, and the patentee of mineral land under Federal statutes, cannot be understood without a knowledge of the situation prior to 1866, and between 1866 and 1872. The Situation before 1866 The western public domain acquired by the United States through treaties, as the result of conquest or purchase, was invaded after Marshall's re-discovery of gold in California, by an overwhelming multitude of prospectors and miners from all parts of the world. The mineral lands of the whole Pacific slope were practically unsurveyed. Congress, disgusted with the experiment of leasing mineral lands; which it had tried for 40 years, and abandoned in 1847, enacted no laws for the management of these public mineral lands, and the pioneers made their own laws governing mining titles. These local regulations applied at first to gulch-mining in the auriferous river-beds only; and they constituted a simple and practical system, adapted to the needs and means of primitive communities-significantly called "camps." They had the means of measuring distances, but not angles; they knew no -property except personal property in the form of pickaxes, pans, supplies, camp-equipage, horses or mules, and mining rights. The earliest codes which they developed expressed what might be called the law of the lariat. With the lariat they measured the distance assigned to each miner along the gold-bearing gulch-a double portion to the discoverer, and a single portion to his successors, in the order of their coming. With the lariat, they hung, after such due process of law as was available, the rascal who stole a horse, or a bag of gold-dust, or a; mining claim, or killed another man without giving him fair notice and a chance to defend himself. In these pioneer codes, adopted in mass-meetings and enforced by the same authority, two features concern us most:

Jan 4, 1914

By J. W. Powell, F. H. Spedding

A complete review of the use of chelating agents in the sepa ration of rare earths by ion-exchange is given as well as a concise description of the recent pilot-plant operations of the Ames Laboratory. The two chelating agents which show the greatest promise are ethylenediamine-N,N,N',N'-tetraacetic acid and N'-(2-hydroxyethyl)ethylenediarnine-N,N,N '-triacetic acid. The first successful separations of rare earths by ion exchange were reported in a collection of papers which appeared in the November, 1947, issue of the Journal of the American Chemical Society.1'9 Some of this work was performed at the Ames Laboratory of the A.E.C., the remainder at the Oak Ridge National Laboratory. The processes developed at Oak Ridge, as well as some of the early Arnes methods, employed 5 pct citric acid-ammonium citrate eluant at low pH and were carried out on either H+-state or NH:-state resin beds. These techniques were successful for the separation of small quantities of either naturally occurring or radioactive rare earths and are still used for the isolation of rare-earth activities from fission products. Concentrated citrate is not economical, however, for use in moderate or large-scale rare-earth separations. For this reason, the Ames Laboratory turned its attention to lower concentrations and higher pH's in order to make more effective use of the eluting agent.10-14 Although elutions have been performed successfully over a wide range of conditions, 0.1 pct citrate at a pH of 8.0 is highly recommended for use on H+-state resin beds.15,16 Elu-tion with 0.1 pct citrate in the pH range from 5 to 9 brings about the separation of the constituent rare earths into a series of flat-topped elution bands which progress down the resin bed, head to tail, without actually pulling apart as do the rare-earth peaks which develop when trace quantities are eluted with 0.25M (5 pct) citrate at low pH's. Because of this, elution with 0.1 pct citrate at pH 8.0 do not produce pure rare earths unless sufficient quantities are present to provide developed bands which are at least several inches long on the columns. Although other eluting agents have proved more effective than citrate solutions, articles concerning the use of citric acid for separating rare earths still appear in the literature occasionally. For example, Ketelle and Boyd17 reported some further studies on the separation of rare earths with 5 pct citrate in 1951. They used 270 to 325 mesh Dowex-50 columns at 100°C and a pH of 3.28. vickery18 compared the effectiveness of a number of eluants for the separation of rare earths on NH+4 state Dowex-50 in 1952. He found that citric acid was more efficient than acetic, malic, tartaric, and aminoacetic acids. In 1953, Mayer and Freiling18 reported that citrate was inferior to malate, glycolate, lactate, and EDTA for the resolution of Sm-Eu and Y-Tb mixtures on 250 to 500 mesh, NH+4-state, Dowex-50 at 87°C. pinta20 used 5 pct citrate in the pH range 2.8 to 3.4 to obtain some rare earths for analytical work the same year. Trombe and Loriers21 reported the use of citric acid in their laboratory to separate rare earths in kilogram quantities. Lariers and Quesney22 reported some separations with citrate in 1954. They used 5 pct citrate at pH 2.8 to separate yttrium and the yttrium-group rare earths from the cerium-group rare earths. briers23 used 5 pct citrate at pH 3.2 and 90°C as late as 1956 to isolate thulium in fair purity. For the separation of tracer quantities of rare earths, Mayer and Freiling19 have recommended pH 5.00, 0.24M lactate at 87 °C on 250 to 500 mesh, NH+4-form Dowex-50. Freiling and Bunney24 have also employed lactic acid for the separation of fission-product rare earths. Cunninghame, Size-land, Willis, Eakins, and Mercer25 have reported a 4-hr separation of Y, Eu, Sm, Pm, Nd, and Pr with 1M lactic acid at pH 3.25 on Zeokarb-225 at 87°C. Stewart, et al.,26 reported separation factors for rare earths distributing between Dowex-50 and 0.25M glycolic acid. stewart27 also reported a 30-61 separation of Y, Tm, Er, Tb, and Lu tracers with buffered, 0.25M glycolic acid containing 0.05 pct Aerosol OT. The resin bed was 400-mesh Dowex-50 (X12). The pH of the ammonia-buffered eluant was 3.5. Various aminopolyacetic acids have also been used to obtain varying degrees of separation of the rare earths. In 1951, Fitch and Russell28 investigated iminodiacetic acid (IDA) and nitrilotriacetic

Jan 1, 1960

By B. F. Oliver, F. Garofalo

Gas-metal heterogeneous reactions and zone-lrelting were sinultarneously employed to produce several high-purity irons with low interstitial contents in a levitating- zone melter. Successive zone-tneltitzg pusses were made in carious sequences of atmospheves which included prepuvified tank hy-drogeta, water vapor hydrogen, palladiuril-purified hydrogen, and vacuunm of 2 x 10-6 Torr. Different irons ranging in purity from 99.89 to 99.996 pct with residual curbon contents of 17, 8 to 10, and 3 to 5 ppm have been Drepared. No measuvable gradient in the residual carbon content was observed along the entire zone-melted length (6-10 in.) in I-ilz.-diameter bars. The absence of a carbon-concentration gradient in the solid indicates an apparent distvihution coefficient of 1, an unusual condition. Internal friction, solid-state extraction, and hot-hardness results indicate that the level of mobile carbon in a iron depends on the gas-metal heterogeneous reactions employed. Purification under an oxidizing atmosphere resulted in the immobilization of nearly all of the carbon present at leuels of 10 ppm or less. Continuation of purification in a reducing atmosphere veturued the carbon to a state of mobility which was aguin reversed by further purification in all oxidizing atmosphere. The immobilization of curbon at "vesidual levels " is believed to be associated with a strong interaction between carbon and oxygen atoms. frons with low carbon and nitrogen contetzts which did not exhibit a hot-hardness peak were produced after zone ynelting in vacuum. CARBON, nitrogen, and oxygen have strong and well-known effects on many properties of iron. These effects persist even at concentrations of 5 to 20 ppm. The intent of the present investigation was to establish procedures for the preparation of high-purity iron with concentrations of these elements in the range of 5 to 20 ppm and lower. The results reported here deal with the procedures employed to prepare high-purity iron, and with observations on the behavior of certain elements at "residual levels": particularly carbon. The details of the (levitating) zone melter in which the final purification steps are performed and the necessary control of the pertinent solidification variables have been described previously.1,2 MATERIALS AND PROCEDURES Commercial electrolytic iron was induction vacuum-melted and cast into 30-lb ingots. Melt additions and ingot analyses for carbon, oxygen, and nitrogen are noted in Table I. All ingots were melted in stabilized zirconia crucibles conditioned with one iron wash heat. Middle sections of the ingots were forged to 1-1/4-in. rounds, machined to 1-in.-diameter bars, then cut to 36-in. lengths. The zone-melting operations were performed on six iron bars (A to F) at a freezing velocity of 2 in. per hr with the freezing interface rotating2 at 200, 300, or 400 rpm. Liquid zones were passed through the bars in various sequences of atmospheres, Table 11, including prepurified tank H2, palladium-purified Hz, wet H2, and system vacuum of 2 x 1018 Torr. Wet-Hz atmospheres were obtained by bubbling palladium-purified Hz through water exhibiting a resistance of 3 megohms. This water was heated with a platinum-immersion heater and was degassed prior to use. Zone melting in a wet-HZ atmosphere resulted in oxidation of the elements which are oxi-dizable with respect to iron. Fine oxide particles were observed on the surface of the liquid zone, and were encased in the bar surface with the passage of the molten zone. Between each zone pass, the surface of the bar was removed by filing and deep etching; this was continued until the oxide formation ceased. The filings were magnetically separated and the residues analyzed by optical spectroscopy. These were especially high in silicon and manganese. Samples were removed from the iron bars, with few exceptions, following each zone-melting operation. A 0.08-in.-thick disc was cut with an Al2O3 cut-off wheel at a point 1/2 in. above the beginning of freezing. Material from each disc was used for hot-hardness measurements, resistivity-ratio measurements, and carbon, nitrogen, and oxygen analyses. Analyses for most other elements were

Jan 1, 1965

By R. F. Mehl, W. Batz, C. Wells

Diffusion coefficient values for carbon in austenite covering a wide range of temperature and composition have been determined employing statistical methods. In addition, the relation between concentration and each of the following, D (diffusion coefficient), Q (activation heat of diffusion), and A (the constant in the diffusion equation), has been obtained. A study of the rates of diffusion of austenite was published in Metals Technology in 1940.' The present investigation is an extension of the earlier work, undertaken (1) to obtain values of the coefficient of diffusion, D, over a much wider range of carbon concentration, and (2) to provide data in all ranges of concentration and temperature in such abundance that statistical methods could be employed to evaluate the accuracy of the data with unusual precision. Composition of Materials: Composition of materials used in this research program are listed in table I. These materials, all forged to about 1 1/4 in. rounds, consist of a high-purity iron, Armco iron, a large number of laboratory-made plain carbon steels containing amounts of impurities normally expected in high-quality commercial steels, and three silicon steels. Since it was known at the time these steels were being made that impurities in the amounts present were unlikely to affect carbon diffusion rates' significantly, the effort made to obtain high-purity steels was not as persistent as it otherwise would have been. Procedure: In general, the procedure followed by Wells and Mehl and described' in detail in an earlier publication' is the one used by the present authors. However, certain modifications have been made which it is believed allow diffusion data to be interpreted more objectively and correctly. These are described completely under appropriate subheadings which follow. Experimental Procedure: Experimental procedure includes (1) the preparation of specimens by welding steels of different carbon contents, (2) the heating of these for certain times at selected temperatures in order to diffuse carbon along the specimens across the welded "interface," and (3) the determination of the carbon distribution across the diffusion zone. Preparation of Specimens: Prior to welding steel of one carbon content to iron or steel of another carbon content, surfaces to be welded are machined perpendicular to the longitudinal axis of cylinders which are about 3/4 in. in diam and 1 1/2 in. long. The prepared, flat, parallel surfaces are brought together and butt-welded electrically. Evidence of a good weld is given in fig. 1. Welding temperature

Jan 1, 1951

By Thomas L. Kesler

IF all of the 14 million tons of kaolin produced in Georgia through 1949 had been mined from a single deposit 20 ft thick, it would represent a mined-out area of less than 1 sq mile. This measure of depletion is in such strong contrast with the large size of the area shown in Fig. 1, from which most of the output has come, that there has developed an optimistic outlook concerning future supplies of kaolin equal in grade to that already mined. Dozens of mines are widely but not evenly distributed within this area, which consists mostly of parts of Twiggs, Wilkinson, and Washington counties. There are scarcely half a dozen kaolin mines elsewhere in the state that have been appreciably productive, although the areas in which they occur may have good possibilities. Most of the efforts to find new deposits, therefore, will be confined to the area shown in Fig. 1, for it is here that the industry has established its facilities, and prospecting is encouraged by relatively numerous outcrops and opened deposits of kaolin.

Jan 10, 1951

By E. A. Anderson

THE copper-zinc phase equilibrium diagram has been the sub-ject of many investigations. Until recently, however, the boundary of the terminal solid solution of copper in zinc (eta) has not been thoroughly investigated. This paper reports determinations of the solid solubility of copper in zinc at temperatures from 100° to 400° C., the course of the liquidus and solidus for the eta solid solution and determinations of the peritectic temperature and peritectic point for the reaction between epsilon and the melt to form eta. The liquidus of the eta phase was determined by thermal analysis and the solidus by the microscopical examination of specimens quenched from temperatures above and below the solidus. The temperature of the peritectic horizontal was obtained by thermal analysis and the com-position at the peritectic point was determined by extrapolation of the solid solubility boundary of the eta phase to the peritectic horizontal. The solid solubility boundary of the eta solid solution was investigated very carefully. Particular care was used to achieve equilibrium in the alloys at each temperature selected. The X-ray, electrical con-ductivity and microscopical methods were used in determining the solid solubility limits. The X-ray method measures the changes in the solvent lattice with increasing solute content and in this manner locates the composition of the alloy at which no further change in the solvent lattice takes place, the limit of solid solubility. The method of electrical conductivity measures the conductivity of the alloys of a graded series of compositions, whereby the solubility limit is indicated by a discontinuity in the conductivity-

Jan 1, 1934

By Hugo L. Johnson, Robert Wallace

THE Midvale plant of the United States Smelting Refining and Mining Company consists of a flotation mill for concentrating sulphide ores of lead and zinc by differential flotation to produce three separate concentrates, one of lead, one of zinc, and one of iron pyrite; and a lead smelter for smelting ores and concentrates to produce base lead bullion, The plant, including its shops, laboratories, office, railroad yards which serve both mill and smelter, and areas reserved for tailing ponds and slag dumps, covers 646 acres on the right bank of the Jordan River at Midvale, Utah. It is twelve miles south of Salt Lake City and sixteen miles east of the West Mountain mining district at Bingham Canyon from which is drawn a large part of its ore supply. Custom ores are treated as well as the product of Company mines.

Jan 1, 1948