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By P. W. George

This paper presents geological data regarding deposits of over 7,500,000 tons of fine-grained sulphide ore in barite gangue. A series of pyroclastics and arkoses was intruded by sills of quartz porphyry in connection with batholithic intrusions of granite 3 miles from Buchans. Gentle folding, with fracturing acid shearing of tuff beds and intruded quartz porphyry, accompanied and followed the intrusion of granite and porphyry. The sulphide-barite mineralization is localized primarily in fractured and sheared tuff beds, but also in the sheared quartz porphyry. Two structures have proved particularly favorable for mineralization-one, the center of an anticline; the other, a series of weak, incompetent tuff beds intruded by thin sills of quartz porphyry and located between strong beds of arkose. During the folding the weak tuff with intruded quartz porphyry was intensely sheared and contorted and subse-quently mineralized by sulphides and barite.

Jan 1, 1937

By C. G. Dunn, F. W. Daniels

IN recent publications1-5 the existence and behavior of subgrain boundaries in high-purity metals has been clearly brought to light. Lacombe and Beaujardl by means of special etching methods disclosed in polycrystalline sheets of aluminum the existence of substructures differing in orientation by small amounts (about 1/4"). Boundaries of these structures at relatively high temperatures had the remarkable property' of moving about while the ordinary boundaries remained stationary. Cahn2 also observed substructures in bent and annealed single crystals of aluminum, zinc, magnesium, and rock salt. The position of subboundaries could be explained in terms of a dislocation mechanism of polygonization in which dislocations move into lines at right angles to the bent glide planes thereby relieving elastic stresses in these planes. Guinier and Tennevin8,6 disclosed the further interesting feature that polygonized structures coarsened significantly upon prolonged annealing. Somewhat similar subgrain phenomena have been observed in silicon iron of commercial purity. Although some evidence for the development of macro-mosaic structures in silicon iron already has been reported by one of the authors6,7 under the phenom-enological term "crystal recovery," much better evidence recently has been obtained due to improved etching techniques. In addition, phenomena regarding structural changes have been uncovered. The present investigation is divided into three parts: (1) The phenomenon of Laue spot sharpening on annealing cold-rolled crystals, (2) the phenomena of polygonization and subgrain coarsening The material used in the present investigation was high-grade commercial silicon iron sheet of nominal composition, 3.3 pct Si, 0.004 C, 0.011 P, 0.010 S, 0.04 Mn, 0.01 Al, 0.04 Cu, 0.01 Sn. Large single crystals of this material Were prepared for cold-rolling or bending as scheduled. Cold-rolling of 12 pct was carried out on a laboratory 8-in, diam rolling mill. The bending deformations were performed by pressing the crystals between a solid Fig. 2—lllustrative foue patterns to show Laue spot sharpening. a (Left)—Specimen as cold rolled, b (right)—After 48 hr at 1400°C. round bar and a mating half cylinder, both heavily greased. Individual specimens were cut from the deformed crystals, and the cut edges were deeply etched prior to annealing. Laue photographs were made using 40-kv tungsten radiation. The technique used to disclose the various subboundaries was an electropolish and electroetch in a bath of chrome-acetic acid.' The anodic polishing done at 22 v was immediately followed by etching at a reduced voltage, which was dependent upon the nature of the subboundaries. Phenomenon of Laue Spot Sharpening on Annealing Cold-Rolled Crystals Fig. 1 gives the initial and final orientations of the specimens cold-rolled 12 pct. Each specimen was annealed at a temperature and for a time which caused significant structural changes as evidenced by alterations in Laue patterns. Representative Laue patterns and micrographs showing the essential changes are given in Figs. 2, 3, and 4. The essential points to be derived from these illustrations follow: 1. Annealing at 950°C clearly develops a substructure with the orientation of the cold-rolled specimen. 2. The subboundaries formed obviously separate regions of nearly the same orientation. Some of the subboundaries appear as a sequence of dots similar to those observed in aluminum by Lacombe and Beaujard,' but whether this is due to extremely small differences in orientation is not known at present. 3. The substructure coarsens upon prolonged annealing. 4. Prolonged annealing also causes a decrease in orientation spread according to Laue spot sharpening'

Jan 1, 1952

By B. H. Caudle, A. B. Dyes

In a recent publication' it was shown that wells with a free surface in a homogeneous gravity-drainage reservoir have a hyperbolic decline with index n '. This paper reports efforts to extend this theory to practical field cases. As a first step in making the extension, a large number of lease production curves from gravity-drainage fields in the stripper stage were fitted with the general hyperbolic decline equation, q/q, = 1/(1 + y) y and n in each case being determined by statistical methods. It was found that this equation is reliable for decline curve extrapolation for periods up to at least 25 years. The resrilts obtained were disturbing in the sense that values for the index, n, were often smaller than one, which fact leads to the prediction that a well would produce all infinite amount of oil in infinite time. A theoretical investigation based on the results of the previous paper provides a suitable explanation for these low values of n. It suggests that these are obtained if production occurs from two or more layers of diflerent permeabilitv and thicktress or two lnyers having different skin effects. It is predicted that as the more permeable layers are exhausted, the index of decline, n, will rise from a value smaller than 2, to n = 2. A practical method is given for fitting the general hyperbolic decline Eq. 6 to production decline data. When this method is used, the index of decline observed in gravity-drainage reservoirs in the stripper stage when wing only data over early years 01 decline usually agrees quite closely with that determined using data over 25 years or more. This indicates that the hyperbolic decline equation is reliable for predicting behavior of such reservoirs. A method is also suggested for taking into account any changes in the value of the index INTRODUCTION As a result of both experimental work with models and theoretical deductions, it was recently concluded' that wells having a free surface in a homogeneous reservoir producing by pure gravity drainage should have a hyperbolic decline with n = 2. The present report details efforts to extend this work on ideal homogeneous reservoirs to actual field cases. It should be remembered that both the previous work and the present extension are based on the assumption that the reservoir is at very low pressure, and hence, nearly all the potential available for driving fluid to the well is the gravity head. Attempts to apply conclusions of this study to reservoirs which have considerable pressures supplementing the gravity drive may lead to difficulty. WELLS WITH NO FREE SURFACE In a dipping gravity-drainage reservoir such as that shown in Fig. 1, some of the down-dip wells have no free surface. The previous study' showed that the up-dip wells, which have a free surface, should follow Eq. 1. The following approximate analysis, of a type which was justified experimentally for up-dip wells in the work just mentioned, leads to results for the down-dip wells.

By Roland Blanchard

ABSTRACT RECENT discovery at Mount Isa of copper mineralization in commercial amount at a depth of 1000 ft., coinciding with downward termination of ore at about the same depth within the larger silver-lead-zinc lenses that have been the standby of Mount Isa's production to date, has been cited as an example in support of mineral zoning. A previous paper by the author and Graham Hall1 furnished a detailed description of the geology of the ore at Mount Isa as exposed up to that time, but necessarily dealt mainly with the silver-lead-zinc mineralization. Most of the geologic facts that constitute the first half of the present paper were set forth in the previous one in much greater detail, with full supporting evidence for the facts cited. The large amount of underground development (approximately 20 miles) and the extensive exploration carried out by diamond drilling (100,000 ft.) at Mount Isa, added to extensive microscope work conducted over a period of years, both by the company's staff and by others, had made possible the calculation within fairly close limits of mineralogical composition of the principal mineralized block of ground down to 1000-ft. depth, and had established closely the mineral succession, with reasons for deposition of the various minerals in the patterns now occupied by them. The geologic facts as outlined in the previous paper remain as stated; but because substantial development within the new copper ore body and further exploratory diamond drilling within the new silver-lead-zinc area (Race-course) have taken place since that paper was written, statements and figures relating to those two areas in the present paper supersede those furnished in the previous one. The recent work likewise has established more clearly the paragenetic relationship between the chalcopyrite and galena. Evidence confirming the relationship is furnished in the present paper. The facts of ore occurrence at Mount Isa show [ACCEPTED ZONAL SUCCESSION Silver sulphantimonides Galena Sphalerite Tetrahedrite Arsenical sulphides Chalcopyrite Pyrrhotite MOUNT ISA SUCCESSION Chalcopyrite In the main but Silver sulphantimonides wholly Tetrahedriteably not Galenacontemporaneous Pyrrhotite Sphalerite Arsenical sulphides They show further: (I) that instead of the silver-lead minerals yielding to increased zinc in depth, the zinc yields to increased silverlead; (2) no dovetailing of the silver-lead-zinc sulphides into chalcopyrite takes place; (3) despite the large amount of pyrrhotite deposited in the district (estimated at upward of 100,000,000 tons), its deposition took place under moderately low temperature conditions; (4) no evidence has been found for increase in temperature of deposition, with depth, to deepest exploration in ore (1495 ft.). The anomalous condition at Mount Isa, both as to the unorthodox mineral succession and the largely unorthodox pattern of mineral distribution, is explained in the present paper,

Jan 1, 1943

By Susasn Leiter

THAT oxygen in copper has been a source of trouble is well known and that that trouble has been real in the commercial world has been shown by Fuller.1 Moore and Beckinsale's paper2 at the annual meeting of the Institute of Metals in London, 1921, called forth considerable discussion. Prof. T. Turner expressed the opinion that it was not necessary to have cuprous oxide present in sufficiently large quantities to form either globules or seams in order to produce a bad effect if the copper were gassed. This brought up the question of the solubility of oxygen in copper and the authors desired to know whether there were any evidence of such solubility, because their experience was that whenever there was any oxygen in copper it was present in the form of free cuprous oxide, .which was practically always in the form of globules. Later Hanson, Marryat, and Ford3 stated that for all practical purposes cuprous oxide may be regarded as insoluble in copper. However, they found particles of the eutectic to coalesce to form much larger particles. They suggested that cuprous oxide was actually slightly soluble in copper, for it was diffi-cult otherwise to understand the mechanism by which such coalescence could take place. W. E. Ruder, in discussing that paper, said that his experiments had led him to conclude that a slight solubility must exist to allow for the ready coalescence of oxide particles, but conductivity tests convinced him that that solubility was very small. Nevertheless, there appeared to be a state of admixture of oxide with copper that closely resembled a colloidal mixture which at first was mistaken for a true solution and which usually existed at the grain boundaries.

Jan 2, 1926

C. M. Bishop (Aircraft Div., A. V. Roe Cnnada Ltd., Toronto)—Reference is made to the coherency hardening of ß due to ß' and also to the hardening of ß due to a coherent precipitation of the a phase. What is meant by the term "ß'?" Would not the coherency hardening of ß during cooling be due to precipitation of a sub-microscopic dispersion of a, as is the case during reheating a ß-quenched alloy? I feel that these two phenomena are essentially the same mechanism, i.e., precipitation of a from unstable or supersaturated ß. From the text, it would appear that Tables III and IV are intended to show the effect of the martensite transformation on the properties of Ti-Mn alloys. Referring to Table 111, the ß-quenched alloys would contain a greater proportion of retained ß than would the equilibrated alloy. Could not the increase in properties be attributed to this, along with possible coherency hardening of the ß? In the same way, the structures referred to in Table IV contain ß from which they could derive their hardness. It would appear to be difficult, if not impossible, to assess the role of the martensite transformation from the data contained in these tables. F. C. Holden, H. R. Ogden, and R. I. Jaffee (authors' reply)—In reply to the first question raised by Mr. Bishop, the term "ß"' designates an apparent retained-p structure which is harder than it is after the most rapid cooling from the ß field. It is thought to be the result of a coherent precipitation of a. The mechanism by which hardening takes place is undoubtedly the same as that involved in the early stages of aging of a re-tained-p structure, and we are in agreement with Mr. Bishop on this point. The term "ß'" to designate the anomalously hard retained-ß structure was agreed upon at a symposium in 1953." The authors do not agree that the quantity of retained ß and/or ß' in the ß-quenched specimens of Table III is necessarily greater than that of the 600°C equilibrated specimens. The ß-quenched specimen has a structure which appears to be completely a' formed by the martensite reaction. It is recognized that there could be some retained ß (or ß') between the a plates if the M, temperature is below room temperature. This is unlikely for the 3.4 pct Mn alloy where the M, is known to be at about 640°C. Therefore, the increase in strength cannot be attributed to the presence of a greater quantity of coherency-hardened ß, but, rather, the increase in strength must be attributed to the transformation products formed, e.g., a' (martensiti-cally formed a). Concerning the data in Table IV, we agree that it is difficult to estimate the role of the martensite reaction, since the 6.4 pct Mn alloy was retained ß in the quenched condition.

Jan 1, 1955

By E. C. Bain

THE more familiar compositions of iron-carbon-chromium1 and the iron-carbon-tungsten2 systems have been investigated with a degree of thoroughness which has permitted the construction of their three-dimensional equilibrium diagrams; and it is probable that these equilibrium diagrams are sufficiently accurate for the present metallographic needs. Strangely enough, in spite of their importance, the alloys of iron, carbon and manganese apparently have not been investigated in the same systematic manner, and so far as is known, no three-component equilibrium diagram for this system is available. Even iron-carbon-nickel alloys3 have been studied rather more thoroughly; for these the solidus and liquidus surfaces have already been determined, but the solid transformations in this, as in the manganese system, have not been reported systematically. The present paper deals with the constitution at equilibrium of a series of 36 iron-carbon-manganese alloys of commercial purity limited by 1.5 per cent carbon and 15 per cent manganese, a range of compositions including most of the manganese steels. The temperature range of melting has not been determined, nor has the high-temperature (delta iron) ferrite equilibrium been included in the study, it being considered that the more important characteristics of the manganese steels are their ordinary transformations in the solid state. The delta iron region is almost certain to be a small tetrahedron not very different in magnitude or contour from that in the iron-carbon-nickel diagram. It is probably true

Jan 1, 1932

By R. J. Pearce, I. Whittle, J. J. Stobbs

The oxidation kinetics of UCu5 in carbon dioxide have been studied over the temperature range 350° to 850°C. At any one temperature, two successive parabolic rate constants are obtained. Up to 650°C, the temperature dependence of the reaction is snzall and the first parabolic rate constant is higher than the second. At temperatures of 690°C and above, there is a very marked temperature dependence and the second rate constant is the higher. Metallo-graphic examination has shown that attack proceeds via internal oxidation. THE oxidation behavior of the U-Cu intermetallic compound, UCu5, in carbon dioxide was briefly examined during investigations aimed at selecting oxidation-resistant uranium-alloy coatings.' It was found that an extremely thick, coherent scale was formed coated at the scale-gas interface with a thin, apparently continuous layer of copper. A more detailed investigation of the oxidation of UCus has now been made. Previous published work2 has been limited to a brief examination of UCu5 in connection with the oxidation of a U-1 wt pct Cu alloy in carbon dioxide. No attempt was made to explain its behavior, but the work indicated that attack proceeded by intern oxidation, with the formation of a layer of copper on the surface of the specimen. EXPERIMENTAL UCus was prepared by arc melting the stoichio-metric amounts of high-purity copper* and uran-

Jan 1, 1965

By C. H. P. Lupis, R. Hocine, G. Bernard

The necessary and sufficient conditions for the stability of a multicomponent phase with respect to infinitesinzal fluctuations are derived and transformed to be written in terms of activity coeffcients and mole fractions rather than in terms of the customary second deritlatives of the free energy. NECESSARY conditions for the stability of a multi-component system were derived by Gibbs as early as 1876.' However, as the usefulness of these conditions is greatly enhanced by the simplicity of their translation in terms of functions of common usage, the present contribution establishes these conditions in terms of activities or activity coefficients-and mole fractions. It was shown in another article2 that not only may these conditions be used for the prediction of the appearance of new phases, but they may also provide a check on the orders of magnitude of the interaction coefficients involved. "Spinodal" decomposition is said to occur when, at constant temperature and pressure, the system is unstable with respect to infinitesimal fluctuations in composition. As a result, the "phases" which appear may be attained through continuous changes in the system rather than discontinuous ones, and, consequently, the free energy of these phases may be described by a unique continuous free-energy function. For a binary system, the familiar curve of Fig. 1 illustrates the case we wish to extend to a multicom-ponent system. The conditions to be written pertain to the decomposition of a system of n moles into moles of phase moles of phase v, ...hen moles of phase 9, where the phases a, ...v, ...9 are—at least initially-arbitrarily close in composition to that of the original phase. Each A, is positive and since the total number of moles n in the system remains constant: Each phase v contains hv(nl +dnY) moles of component (I), ...xV(ni +dny) of component + dnk) moles of component (m). The total number of moles ni in the system remaining also constant, it is clear that:

Jan 1, 1968

By G. Derge, R. E. Grace

A S detailed studies of mass transport in hetero- geneous systems are made, a knowledge of the chemical diffusion coefficients in various liquid and solid phases is necessary to understand the kinetics of any total reaction. For example, in zone refining some information must be available about the diffusion coefficients of various species in the liquid and solid regions near the moving interface. In liquid-liquid reactions, of which slag-metal reactions are of particular interest to metallurgists, the diffusion coefficient of a transferring species must be known accurately in both phases in order to predict a transfer coefficient for the over-all process. Diffusion data for various elements in liquid iron and iron-carbon alloys have been roughly deter-

Jan 1, 1959

By C. F. Jr. Nagel

THIS paper is written primarily for those who are familiar with the processes mentioned but who desire a further insight into some of the fundamental principles. It does not give a complete description of the various practices employed in the working of aluminum and its alloys, but presents a few illustrations of the essential respects in which aluminum differs from other common metals, and emphasizes the controlling factors of the processes under consideration. HEAT TREATING Certain aluminum alloys are capable of having their mechanical properties greatly altered by a heat-treatment process. The degree of this improvement may be illustrated by the typical properties of duralumin (Table 1). It is essential that the material be in the wrought condition in order to obtain maximum heat-treatment effects.

Jan 1, 1927

By Howard Reiss, C. S. Fuller

A theoretical and experimental study has been made of those interactions between holes and electrons which influence the solubilities of donors and acceptors in semiconductors. The major portion of the work concerns the solubility of lithium in silicon doped to varying degrees with boron. This solubility increases with increasing boron content in a manner predicted by theory and exhibits the expected temperature dependence. A qualitative experiment in germanium is described which demonstrates, in accordance with theory, that doping with a donor decreases the solubility of another donor. SEVERAL authors have discussed the possibility that holes and electrons behave like chemical entities and influence the solubilities of ionized impurities, Wagner was the first to invoke this concept in connection with his studies on nonstoichio-metric oxides. He used it again in explaining the solubility of hydrogen in molten binary alloys. In a theoretical paper,' Reiss drew attention to the fact that solutions of impurities in semiconductors

Jan 1, 1957

By H. L. Brunjes, G. B. Gould

The softening temperature of coal ash, as determined in the laboratory, has been used for years as an indication of the tendency of coal to form clinker and slag. It has not, however, provided an index of unfailing and complete reliability for forecasting the relative performance of different coals, even in the same plant and under the same conditions of operation. A large amount of investigation has been done in attempts to account for this, but practically all of this has been in the direction of studying the chemical constitution of coal ash. Much has been learned, but without much progress toward a better practical application of knowledge to the selection of coal. There has always seemed to be an important factor that eluded discovery. It has long been recognized that the ash-softening temperature as determined in the laboratory had one weakness, in that it represented the temperature at which a thorough mixture of the whole ash of the coal would melt, the mixing having taken place before the heal was applied. This does not, of course, simulate what takes place in practice. With certain exceptions, which will be noted later, almost all of the investigations that have been made, especially the chemical studies of coal ash, have likewise dealt with a mixture of the whole ash in the coal. The present investigation differs from these fundamentally in its approach to the problem. It started from the observation that some clinkering and slagging obviously takes place in a boiler furnace at temperatures below the laboratory-determined ash-softening temperature of the coal. Knowing that coal as it is shipped to market is a heterogeneous mixture of diverse mineral substances, each of which may act independently of the others in the initial stages of clinker and slag formation, it seemed logical to investigate separately the softening temperature of the ash in physically separable portions of the coal, and to determine the relative quantities of ash contributed by each portion. While the data are far from complete, covering as they do only a few coals, and while the conclusions to be reached from the data at this stage arc, in some measure, speculative, they are presented at this time because

Jan 1, 1940

By G. B. Gould, H. L. Brunjes

The softening temperature of coal ash, as determined in the laboratory, has been used for years as an indication of the tendency of coal to form clinker and slag. It has not, however, provided an index of unfailing and complete reliability for forecasting the relative performance of different coals, even in the same plant and under the same conditions of operation. A large amount of investigation has been done in attempts to account for this, but practically all of this has been in the direction of studying the chemical constitution of coal ash. Much has been learned, but without much progress toward a better practical application of knowledge to the selection of coal. There has always seemed to be an important factor that eluded discovery. It has long been recognized that the ash-softening temperature as determined in the laboratory had one weakness, in that it represented the temperature at which a thorough mixture of the whole ash of the coal would melt, the mixing having taken place before the heal was applied. This does not, of course, simulate what takes place in practice. With certain exceptions, which will be noted later, almost all of the investigations that have been made, especially the chemical studies of coal ash, have likewise dealt with a mixture of the whole ash in the coal. The present investigation differs from these fundamentally in its approach to the problem. It started from the observation that some clinkering and slagging obviously takes place in a boiler furnace at temperatures below the laboratory-determined ash-softening temperature of the coal. Knowing that coal as it is shipped to market is a heterogeneous mixture of diverse mineral substances, each of which may act independently of the others in the initial stages of clinker and slag formation, it seemed logical to investigate separately the softening temperature of the ash in physically separable portions of the coal, and to determine the relative quantities of ash contributed by each portion. While the data are far from complete, covering as they do only a few coals, and while the conclusions to be reached from the data at this stage arc, in some measure, speculative, they are presented at this time because

Jan 1, 1940

By Werner Ostertag

A series of rare earth cobalt compounds of the composition RCoa (r = Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Ev, Tm, Lu) has been prepared. The compounds crystallize in space gvoup R3m and are isomorphous with PuNi3. Except for CeCo3 and PrCo, the series shows decreasing- values of a. and co. The relalively small parameters of CeCo, and PrCo, are explained by valencies of cerium or praseodymium which exceed the usual rare earth valency of three. The structure of the compounds is discussed as in-fillings of kagome nets in direct and staggered superposition. In the course of a systematic investigation of rare earth cobalt compounds"2 and their magnetic properties,, a series of alloys corresponding to the formula Rco3 has been prepared. The investigation of the Rco3 series was stimulated by our investigation of the yttrium cobalt system2 as well as by reports in the literature: Smith and Hansen4 reported the structure of YcO3 and Van vucht5 that of GdCo3; ceco3,6 Gdco3,7 and DyCo3 7 have been found to be single-phase during phase diagram studies. It was the purpose of this work to report crystallographic data on the entire Rco3 series and to interpret the structure of these compounds on the basis of general principles as discussed by Frank and Kasper.8 At the time this work was terminated, it was learned that a similar investigation has been carried out independently by Bertaut, Lemaire, and schweizer.9 Except for CeCo3 (ao = 4.952, co = 24.73') and NdCo3 (a0 = 5.067, co = 24.76') data of this work are in satisfactory agreement with their investigation. EXPERIMENTAL TECHNIQUES A series of samples having the composition Rc03 was prepared from stoichiometric amounts of the rare

Jan 1, 1968

By D. L. Albright, G. A. Colligan

An investigation has been conducted to determine the nature of the crystallographic substructure of nickel and a 1.0 wt pct Ag-Ni alloy which had been undercooled 105°C prior to solidification. A rotating back-reflection X-ray technique and modified Weissmann diffractometer were used to orient single-crystal sections from these poly-crystalline ingots and to determine the substruc-tural features of these single crystals, The sub-grain size in the pure nickel ingot is 0.5 mm diam while the silver-doped nickel subgrain size is only 0.1 mm diam. The misorientation between adjacent subgrains is approximately 1 deg of arc in both ingots, and the spread of orientation of sub-grains about the mean orientation of the crystal is 5 deg of arc in both ingots. The addition of silver results in a stable impurity substructure which is preserved during isothermal solidification and subsequent cooling to room temperature. In the absence of silver the initial impurity substructure is destroyed by dislocation interactions which produce a secondary substructure which grows to a size five times larger than the initial substructure. THE process of undercooling a metal entails cooling of the molten sample below the equilibrium freezing point without the occurrence of solidification, i.e., by exercising proper constraint over the experimental variables contributing to nucleation in the melt. The current work of walker1 and Colligan Metal reports undercooling large continuous samples of nickel by imposing appropriate restrictions upon the parameters of solidification. The silver-nickel equilibrium diagram3 reveals the presence of a monotectic reaction at 1435°C. At this temperature the maximum solid solubility of silver in nickel is approximately 3 wt pct, but this solubility decreases with decreasing temperature and the solute is rejected as a silver-rich liquid phase at temperatures below 1435°C. Thus, the 1.0 wt pct solute should be held in solution during undercooling and solidification and subsequently precipitate as a silver-rich liquid phase at grain and subgrain boundaries following solidification during cooling below 1435. This assumes no solute segregation sufficient to cause the monotectic reaction. One would expect this second phase to inhibit grain and subgrain growth by retarding dislocation motion after solidification is complete. The effectiveness of silver addition in growth retardation of high-angle grain boundaries has been demonstrated by Colligan and suprenantS4 The principal [l00] dendrite growth directions in a 2 wt pct Ag-Ni alloy undercooled 53 all radiated from the nucleation site. A similar pure nickel ingot undercooled 59°C exhibited a random orientation of [l00] dendrite directions with respect to the nucleation site. Since undoped nickel ingots do not retain any evidence of the casting or solidification texture and silver-doped ingots do retain this texture, it is reasonable to assume that considerable grain growth has taken place in the pure nickel. These particular experiments were performed in order to reveal the differences, if any, in the features of the crystallographic substructure of undoped undercooled nickel and silver-doped undercooled nickel. 1) EXPERIMENTAL PROCEDURE Data are reported on selected specimens from two massive (approximately 260 g) undercooled ingots of nickel. One ingot consisted of electrolytic nickel and the other of this same material with 1.0 wt pct addition of high-purity silver. Powder patterns were taken of both the as-received and as-solidified materials; in all cases the reflections recorded were attributable to the individual elements nickel and/or silver. Fig. 1 is a. schematic diagram of the apparatus employed for the undercooling experiments. The equipment consists in part of a fused silica crucible for containing the charge. A fused silica tube encloses the system, which is covered by a brass cap to permit partial sealing of the inert atmosphere. This cap contains a hole through which a Pt-Pt 13 pct Rh thermocouple is inserted for temperature measurement. The charge is inductively heated under a purified argon atmosphere.

Jan 1, 1963

By George W. King

The yield strength of a dispersion-hardened W-3.8 vol pct Tho,alloy, in both the recovered and recrys-tallized condition, was investigated and cornpared with that ofrecrystallized pure tungsten over the temperature range of 325" to 2400°C. It is deduced that the Orowan mechanism is obeyed in the recrystallized alloy. In the recovered alloy, a further enhancement of the yield strength results from the retained substructure which is stable up to temperatures in excess of 2700°C. Temperature and strain rate cycling tests were also performed, and the apparent activation energy for the deformation process was derived. This activation energy, - 3 ev, for the recovered and also the recrystallized alloy was about the same as that for re crystallized pure tungsten. However, the activation volume of the recovered alloy, -10-2 cu cm, was about an order of magnitude lower than that of the recrystallized alloy or pure tungsten. This fact accounts for an enhancement oj- the temperature dependence of the yield stress of the recovered alloy. A dislocation velocity exponent of about 4 to 13 was deduced frorn the strain rate cycling tests , which is in good agreement with values reported for tungsten single crystals. VARIOUS theories have been developed to explain the enhanced yield strength of a metal containing a dispersed second phase of small hard particles. These theories are thoroughly reviewed by Kelly and Nicholson.' The theoretical models can be separated into two types. The first type assumes direct interactions between moving dislocations and dispersoids. One of the most widely investigated models for this mechanism is the bowing out of dislocations between the dis-persoids and their subsequent pinching off in order to bypass the obstacles. This is the well-known Orowan mechanism.' The second type is an indirect effect of the dispersion because of its ability to stabilize to high temperatures the substructure introduced by cold working. In this instance, the increment in the yield strength is expected to be inversely proportional to the square root of the subgrain diameter. In the present work, a quantitative study was made of the strengthening effect caused by a thoria dispersion in a recrystallized W-3.8 vol pct Thoz alloy over the temperature range 325" to 2400°C. The results are compared with the increment predicted for the Orowan mechanism based on the calculations by ~shb~.~ In addition, the alloy was tested in the recovered state so that any additional strengthening resulting from the substructure produced during fabrication could be measured. The respective contributions can be separated in this manner, provided that the particle size distribution of the dispersion remains the same in both the work-hardened and the recrystallized state. Particle size distribution measurements showed that this condition was met in the present work. I) EXPERIMENTAL PROCEDURES A) Material Production and Fabrication. The alloy investigated is essentially the same as that reported much earlier by ~effries,~ who also found the strength of tungsten to be improved by the thoria dispersion. The procedure for producing the alloy consisted of mechanically blending a thorium nitrate solution in proper concentration with tungsten oxide (WO3) powder, followed by hydrogen reduction to metal powder. After reduction, the dispersed second phase is present as thoria (Thoz). The pure tungsten powder used for comparison was produced in the same manner except that the thoria doping step was omitted. The powders were consolidated by cold pressing and self-resistance sintering in hydrogen. The resulting ingot had a cross section about 0.6 sq in. and a density about 93 pct of theoretical. The ingot was swaged to 0.174-in.-diam rod at temperatures varying from 1650°C initially to -1200°C near final rod sizes. Two intermediate recrystallization anneals were employed during fabrication. Analysis of the swaged rods is reported in Table I. B) Electron Microscopy Techniques. Carbon extraction rrPxcas prepared by a technique reported by ~00' were used to quantitatively evaluate the thoria particle size and distribution. Electron nlicrographs of extraction replicas were taken at 20,000 times but were then enlarged two to three times in printing. The areas photographed were randomly selected. A Zeiss Particle Size Analyzer (Model TGZ3) was used to count and measure the sizes of all particles present on the print. About three thousand particles were counted in determining a distribution curve. Electron transmission microscopy was used to determine the effect of annealing on the substructures of the materials. Thin foils were produced by a two-stage thinning process. The rods were first ground on emery paper to ribbons about 10 mils thick and then a jet of 5 pct KOH was used to electrolytically reduce a portion of the cross section of the ribbon. Final perforation was achieved by immersing the specimen in a 5 pct KOH solution and electrolytically polishing at a current density of about 0.3 amp cm-'. The foils were examined with a Hitachi HU-11A electron microscope. C) Tensile Testing. Tensile testing was performed in an Instron Testing Machine equipped with a radiation-type vacuum furnace which operates at about 1O"S torr at temperatures as high as 2400 °C. The same furnace was used for annealing the tensile specimens.

Jan 1, 1970

By Paul T. Allsman, E. W. Newman

Trenching, sampling, and core drilling in Stillwater and Sweetgrass Counties, Mont., by the Bureau of Mines have delimited over 5,000,000 tons of chromite ore containing more than 20 per cent chromic oxide. The Benbow and Mouat-Sampson mines have been developed and are fully equipped for mining and milling 500 tons and 2000 tons a day, respectively. Introduction The Montana chromite deposits were the first to be explored under the Strategic Minerals Act of 1939. In June of that year, the Bureau of Mines started exploration by trenching, test pitting, sampling and diamond drilling, and completed the project in March 1943. The U. S. Geological Survey cooperated by mapping the geology and logging the cores. The project was to determine the extent and grade of the chromite ore and to indicate sufficient reserves to justify development and exploitation of the deposits for the national emergency. Exploration has indicated that the district contains the largest and most important reserve of chromite ore in the United States. The Benbow and Mouat-Sampson mines have been developed and a 500-ton concentrating mill has been constructed on the Benhow property and a 2000-ton mill on the Mouat-Sampson property. Concentrates were produced from the Benbow mill three months after the attack on Pearl Harbor, when the nation's major chromite supplies from foreign sources were cut off. History It has been known for 50 to 60 years that some chromite deposits existed in an east-west belt along the north escarpment of the Beartooth Mountains about 25 miles north of Yellowstone Park, but nothing was known of their size and extent until the war demand of 1917 and 1918 stimulated the search. In those years two properties in the Stillwater region were actively developed, but no shipments were made. The Benbow property was located in 1918 by a local group. The property comprised seven claims along the strike at the east end of the belt. An adit was driven several hundred feet on the Eclipse claim. The seven claims were sold to the Chromium Products Corporation of Livingston, Mont., and were subsequently patented. In 1929, an eastern group obtained an option, installed some equipment, and erected several log cabins. The "crash" in the market in 1929 caused the operators to drop their lease, and the property remained inactive until 1939, when the Bureau of Mines began its exploration. Fourteen claims were located on the Boulder River in 1918 and subsequently patented by the U. S. Chrome Corporation.

Jan 1, 1949

By Paul T. Allsman, E. W. Newman

Trenching, sampling, and core drilling in Stillwater and Sweetgrass Counties, Mont., by the Bureau of Mines have delimited over 5,000,000 tons of chromite ore containing more than 20 per cent chromic oxide. The Benbow and Mouat-Sampson mines have been developed and are fully equipped for mining and milling 500 tons and 2000 tons a day, respectively. Introduction The Montana chromite deposits were the first to be explored under the Strategic Minerals Act of 1939. In June of that year, the Bureau of Mines started exploration by trenching, test pitting, sampling and diamond drilling, and completed the project in March 1943. The U. S. Geological Survey cooperated by mapping the geology and logging the cores. The project was to determine the extent and grade of the chromite ore and to indicate sufficient reserves to justify development and exploitation of the deposits for the national emergency. Exploration has indicated that the district contains the largest and most important reserve of chromite ore in the United States. The Benbow and Mouat-Sampson mines have been developed and a 500-ton concentrating mill has been constructed on the Benhow property and a 2000-ton mill on the Mouat-Sampson property. Concentrates were produced from the Benbow mill three months after the attack on Pearl Harbor, when the nation's major chromite supplies from foreign sources were cut off. History It has been known for 50 to 60 years that some chromite deposits existed in an east-west belt along the north escarpment of the Beartooth Mountains about 25 miles north of Yellowstone Park, but nothing was known of their size and extent until the war demand of 1917 and 1918 stimulated the search. In those years two properties in the Stillwater region were actively developed, but no shipments were made. The Benbow property was located in 1918 by a local group. The property comprised seven claims along the strike at the east end of the belt. An adit was driven several hundred feet on the Eclipse claim. The seven claims were sold to the Chromium Products Corporation of Livingston, Mont., and were subsequently patented. In 1929, an eastern group obtained an option, installed some equipment, and erected several log cabins. The "crash" in the market in 1929 caused the operators to drop their lease, and the property remained inactive until 1939, when the Bureau of Mines began its exploration. Fourteen claims were located on the Boulder River in 1918 and subsequently patented by the U. S. Chrome Corporation.

Jan 1, 1949

By J. F. Smith, J. R. Ogren, N. J. Magnani

The uapor pressrcres of magnesium over binary alloys of magnesium with twelve of the yare-earth eletnetzts have been measured by the Knudsen effuion method in the temperature range 675° to 910°K. These vapor-pressure measurments were combined with data concerning the tevtrlitzul magnesium solubility and the vapor pressure of pure magnesinm to evaluale the standuvd free energies of pluase jormation. These free-etzergy values indicate that the CsCl structures of the heacy rave earths tend to be somewhat less stable than those of the light rare earths. This dif-]eying- behaviov covrelates with differences which have been obsevz~ed in other alloy systetns wherein a phuse appeurs, disappeavs, or changes crystal stvucture as the atomic number of the rare-earth com-ponent is changed. This behauior also appears to correlate with the struclurul rariations within the rare-earth elements themselves, and it is speculated that cariations in the spatial extent of the 4f orbitals are responsihle. STUDIES of the phase relationships and crystal structures in the binary systems between rare-earth metals (lanthanons) and magnesium are extensive but far from complete. However, the currently available information1-10 does produce a rather interesting pattern. This is illustrated in Table I. If one excludes europium and ytterbium from consideration because of their generally atypical behavior, it can be seen from the table that the phase relationships in the magnesium-rich regions show a distinctly different pattern for the lighter lanthanons as compared to the heavier lanthanons. For the lighter lanthanons, LnMg2 phases occur from lanthanum to gadolinium with the cubic MgCu2 structure, LnMg3 phases occur from lanthanum to terbium with the BiLi3 structure, and magnesium-rich phases occur from lanthanum to gadolinium with stoi-chiometries between Ln5Mg42 and LnMg12. In contrast, for the heavier lanthanons, those LnMg2 structures which have been examined have the hexagonal MgZn2 structure, LnMg3 phases have not been observed beyond terbium, and the magnesium-rich phases occur with the a manganese structure near a stoichiometry of Ln5MgZ4. The heavy lanthanon-magnesium systems thus appear to be analogous to the Y-Mg system""2 wherein YMg has the CsCl structure, YMg2 has the MgZn2 structure, and the region Y4Mgz5-Y5Mg24 has the a manganese structure, and no other intermediate phases are observed. Similarity in alloying behavior between yttrium and the heavy lanthanons occurs commonly, and on this basis it seems likely that LnMg2 phases will be found with the MgZn2 structure in the binary systems of dysprosium, thulium, and lutetium with magnesium when the appropriate investigations are made. In the case of the magnesium-rich phases of the lighter lanthanons, only the Ce-Mg phase relationships have been investigated thoroughly and in detail, and until similar investigations are made for the other systems there will remain questions as to which magnesium-rich stoichiometries represent equilibrium phases and what systematic variations occur in the sequence from lanthanum to gadolinium. Thus the data in Table I show that only the LnMg phases occur with the same crystallographic structure throughout the sequence from lanthanum to lutetium. It was speculated that the relative stability of these LnMg phases might vary from one lanthanon to the next in such a way as to presage the differences which occur among the more magnesium-rich lanthanon-magnesium phases. On this basis the present investigation of the thermodynamics of phase formation was Gndertaken for the LnMg phases. PROCEDURE AND RESULTS A generalized phase diagram for the lanthanon-rich portion of a lanthanon-magnesium alloy system is shown in Fig. 1 where ß represents a high-temperature bcc

Jan 1, 1968