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By N. A. Zeigler

Considerable work has been and is being done on the changes of physical properties that take place in alloys at elevated temperatures, and much information on this subject is published. Much less is known, as pointed out by Rickett and Woodll about reactions between the alloys and atmospheric gases and still less is known abut changes within the alloy itself under the influence of heat and given atmosphere. Moreover, most of the work published has been done on the alloys of "heat-resisting" type, in which chromium is an essential ingredient, the behavior of all other alloys being quite unknown, except perhaps of decarburization produced at the surface by oxidizing atmospheres. It has been shown2 that iron, with total amount of foreign ingredients not exceeding 0.01 per cent, if heated in an oxidizing atmosphere at above 900" C., may be saturated with oxygen to 0.1 per cent. It was suspected that something of a similar nature may take place in iron-silicon alloys (transformer material), the mechanism of such processes being either a direct diffusion of oxygen into the alloy, or oxygen combining with silicon to form SiO2 or more complicated (silicate) inclusions. Another possibility to be considered was that during annealing in oxidizing atmospheres, when scale is being formed, silicon may oxidize preferentially at the surface, thus impoverishing the alloy in silicon. In collaboration with Dr. T. D. YensenP3 the writer set out to investigate this problem about two years ago in order to settle these questions. Testing Procedure In the first part of the investigation, two pieces of 4 per cent silicon iron, prepared in hydrogen atmospheres and forged to 3/4-in. square bar,

Jan 1, 1934

By James W. Dally, William L. Fourney, Anders Ladegaard Peterson

For the past 3 years, the authors have been conducting research sponsored by the National Science Foundation (RANN) to improve the process of excavation by drilling and blasting. The approach followed has been experimental where the development of stress waves and fractures initiated at the bore hole have been investigated in order to obtain a complete understanding of the dynamic Fracture process. The second step in the approach has been to introduce modifications in the drill and blast procedure which will permit closer control of the fracture process.

Jan 2, 1978

By B. H. Kear, H. G. F. Wilsdorf

After a few percent strain, dislocations in disordered Cu3Au are arranged in groups in ulell-defined slip planes, which contrasts with the more or less random distribution of dislocations in the corresponding ordered alloy. Unusually long and straigkt dislocation segments observed in the ordered alloy are interpreted in terms of cross slip of screw dislocations from their slip planes into cube planes. It is proposed that cross slip, and also dislocation reactions of the Lomer type, play an important role in work hardening of the ordered alloy. ACCORDING to to dislocations in the disordered lattice are only partial dislocations in the corresponding super lattice, so that in the super-lattice dislocations must occur as pairs, with each pair connected by a ribbon of antiphase boundary. Recently, striking confirmation of the theory was obtained by Marcinkowski, Brown, and Fisher3j4 in a study of dislocation configurations in thin foils of the Cu3Au alloy by transmission electron microscopy. In the present investigation, the observations made by these workers have largely been confirmed. Moreover, it has been found that dislocations in the plastically deformed ordered alloys are often unusually long and straight. This paper is mainly concerned with these new observations. A tentative explanation is offered in terms of cross slip of dislocations in the ordered alloys. PREPARATION OF SPECIMENS An alloy close to the stoichiometric composition Cu3Au was prepared by melting together high-purity copper and gold (99.995 pct) under vacuum in a graphite mold. The resulting ingot was rolled down and cut into strips 1 1/2 by 1/8 by 0.005 in. in thickness. All strips were annealed at 900°C for 3 hr and cooled to 500'~. A few of the strips were quenched from ~OO'C, while the remainder were slowly cooled in the temperature range 400" to 150°C at intervals of a few degrees every 24 hr to produce a high degree of order. After this annealing treatment the average grain size of the material was about 0.1 mm. Material in different states of order was obtained by reannealing fully ordered material at temperatures below the critical temperature: followed by quenching. The equilibrium degree of order attained at a particular reannealing temperature was obtained from the paper by Keating and warren.' A simple hand-operated tensile jig was used to give the strips the required amounts of plastic strain. Following straining, a number of specimens were cut from each strip by means of an electrolytic cutting device.= Finally, each specimen was thinned electrolytically using the polishing procedure described by Bakish and Robertson,7 and these thin sections were examined in the Philips EM-100B electron microscope operating at 100 kv. EXPERIMENTAL OBSERVATIONS Antiphase boundaries. The average domain size in the ordered alloys was found by direct observation to be about 0.25 p. Also, it was observed that the grown-in configuration of antiphase boundaries was changed little by plastic deformation, at least up to 6 pct strain. Fig. 1 shows an electron micrograph of a thin foil of partially ordered alloy (S - 0.8) after 3 pct strain. The micrograph shows a few dislocation pairs and a somewhat crystallo-graphic network of antiphase boundaries. The normal to this foil was found by diffraction analysis to be approximately 11121, with principal directions in

Jan 1, 1962

By C. M. Haight

The mines of the New Jersey Zinc Co. in New Jersey, are situated in the northern part of Sussex County, at Franklin, formerly Franklin Furnace, and also at Ogdensburg. The mine at Ogdensburg is still in the development stage, but the, mine at Franklin, with which this paper deals chiefly, has been a steady producer of high-grade zinc ores for many years. The town is about 50 miles from New York City, among the foothills -of the Kittatinny Mountains. It is equipped with water supply (filtered and chemically treated), good roads, electric lights, efficient police protection and excellent schools, including a new vocational high school. For a mining community, the conditions and location are far above the average. Franklin Furnace Folio, No. 161 of the U. S. Geological Survey, describes the geology and mineralogy of the district in detail, so that merely an, outline of the main characteristics of the orebody need be given. The

Jan 10, 1917

By J. W. Hickman

INTRODUCTION MOST of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.1 In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,2 nickel,2 chromium ,2 Copper2, tungsten,3 molybdenum,3 beryllium ,4 uranium,4 thorium4 titanium5 and zirconium5 while investigations are in progress on tantalum and columbium, The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single, phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally, Examples of solid solutions which may present difficulties are MoO2 and W02, Fe3O4 and FeO-Cr2O3 since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of log10 KR for the several temperatures. [OF°R = -RT In KR 0 and-~75T = logi°KR] [?F°R] and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the values given in Table I to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium' oxide to form

Jan 1, 1948

By Walter Harvey Weed

Introductory.............449 Summary oF Types............452 I. The Virgilina Type...........452 The Virgilina mines...........452 Location.............452 History.............453 The rocks of the district..........453 The veins.............454 Notes on the mines.... 458 The Holloway. 458; Yancey and Durgy. 465 ; Copper World. 467 ; Frazier. 467 ; Thomas. 467 ; Anaconda. 468; Blue Wing. 468; High Hill. 472; Dorothy.......474 II. The Gold Hill Type...........474 The Gold Hill mine...........475 Location.............475 History............• 475 Surface improvements.......... 476 The rocks............478 Vein.phenomena...........478 Character of the ore..........481 Origin of the ore...........481 Notes on the mine.workings.........482 Other occurrences of ore-deposits of the Gold Hill type.. .. 483 III. The Ducktown Type..........484 The Ducktown mines...........485 Other examples of the Ducktown type....... 494 Alabama mines...........494 North Carolina examples : Ore Knob.......496 Virginia examples..........497 IV. The Catoctin Type.. ......... 498 General characteristics,......... 498 The Linden district...........499 General distribution of the Catoctin type.......503 Introductory. In the early history of this country the existence of copper in the Appalachian region was well known. but no mining mas attempted until the discovery of the Ducktown deposits in

Jan 1, 1901

By H. S. Martin

THE Phosphate Recovery Corporation operates three flotation plants, Nos. 1 and 2 concentrators about three miles northeast of Mulberry, Florida, and No. 3 plant at Wales, Tennessee. These plants represent the first commercial phosphate flotation operation and are also believed to be the largest nonmetallic flotation operation in the world at the pres-ent time. The details of this paper will be confined to plant No. 2, this being the newest and largest concentrator in Florida, and the flow sheet being practically the same as at plant No. 1. The No. 3 plant has been oper-ated but a short time and has been shut down since December, 1932, on account of the decrease in phosphate rock production. The phosphate washers usually are located centrally on a known deposit so that about two hundred acres of ground can be mined eco-nomically to each washer location. The washers are moved to new areas when the distance becomes too great for economical pumping. The flotation plants are built either adjacent to a washer, so that current debris may be utilized, or on the site of a former washer where there is sufficient accumulated debris available for mining, and the flotation plants must also be moved from time to time. Most of the water used in the Florida flotation plants is recovered after passing through a circulating system where most of the fine sus-pended matter is settled out, but some make-up water is obtained from deep wells near the plant. Power is obtained from the Tampa Electric Co. through the dis-tribution facilities of the International Agricultural Corporation. Flotation concentrate is hauled from the plant by trolley over the International Agricultural Corporation's trolley system, to the drying plant at Prairie, one mile northwest of Mulberry.

Jan 1, 1933

Sec. 1. The membership of the Institute shall comprise six classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members. All shall be equally entitled to the privileges of membership, excepting that no member of any class whom residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the claw of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members.

Jan 1, 1941

H. W. Turner, San Francisco, Cal. (communication to the Secretary*): This excellent paper apparently represents the results of extensive observation and experience among the mines of the Mother-Lode, but I strongly question its relegation of the dioritic intrusions to the period of fissuring and ore-deposition. The dioritic rocks referred to are evidently those areas represented by Ransome in the Mother-Lode folio1 as meta-diorites, and, as he says, are merely basic facies of the great granodiorite batholite of the Sierra Nevada. If followed downward I venture to predict that these meta-diorite areas would be found to connect with the great batholite, and to be in fact mere apophyses of it. I see no reason for supposing that these apophyses were intruded into the Mother-Lode slates at a period later than the intrusion of the granodiorite in general. The period of fissuring was subsequent to this intrusion; the basic granodiorite or quartz-diorite areas of the foot-hill region are themselves fissured extensively; and the fissures were filled with quartz, apparently during the same general period of the formation of the Mother-Lode veins. Prichard and Ransome2 both refer to the deposition of quartz in the same lode at different periods resulting from a reopening of the fissures. Some time since, I saw in the stopes of the

Jan 1, 1904

By R. U. Fitting, A. C. Bulnes

Field experience with limestone and sandstone production indicates the existence of wide differences between the reservoir behavior of these two types of formation. Little attention appears to have been given to the separate study of the flow of fluids and the retention of fluids in limestones. This paper presents data and arguments to demonstrate the existence of a difference between the two types of formation, and urges the separate intensive investigation of limestone reservoirs. AH experimental data presented pertain to dolomitic limestone formations in west Texas and New Mexico. Two kinds of Porous media are recognized— intergranular and intermediate. Intergranular rocks are those in which the porosity and permeability are determined by the geometrical properties and the sorting of the sedimentary units; intermediate rocks, those in which there is no direct relationship between grain properties and the porosity and permeability. Limestones in general are intermediate media. The partial relationship between porosity and permeability of any class of Porous media is represelried by an area of .finite extent and definite shape on the permeability-porosity plane. The horizontal and vertical variations of porosity and of permeability in limestone and sandstone formations are discussed and compared. Comparisons are made of connate-water content, the relative permeability-saturation relationship, and capillary phenomena in the two kinds of rocks. A number of tentative conclusions are drawn relative to the reservoir properties of lime- stones; in particular, (I) dolomitic limestones are oil bearing and apparently are oil productive in zones of permeability less than 0.1 millidarcyj and (2) primary depletion (by gas expansion) oil saturations may be lower in dolomitic limestones than in sandstones. Introduction It is well known that the reservoir performance of limestones displays numerous irregularities when compared with that of sandstones, and that the departures from "normal" behavior of limestones are more frequent and generally more marked than in sandstones. This is particularly true of fractured limestones and those that have undergone considerable development of secondary porosity' A review of the literature of production research published during the past 15 years reveals a startling absence of theoretical and experimental investigations directed specifically toward explaining and predicting the performance of limestone reservoirs, even. though such problems as the prediction of water encroachment and the estimation of ultimate recoveries continue at the "inspired guess" stage. By far the greater part of the experimental data reported pertain to measurements on sandstone core samples, while the theoretical studies, almost without exception, are developed from the assumption of an ideal porous medium and therefore seldom are applicable to limestone formations. The chief cause of this situation appears to be the common belief that, to all practical intents and purposes, sandstones and the majority of producing limestone formations

Jan 1, 1945

By J. B. Goddard

The discovery of rhenium on the ion exchange resin used at the uraniun in-situ leach operations at Palangana, TX, led to a laborabory study of possible recovery methods. Rhenium was present in small amounts in the ammonium carbonate leach liquors as the perrhenate anion, ReO4-. It concentrated on the anion exchange resin, which was a factor of 10 more selective for rhenium than for uranium. Various elution systems were investigated for stripping the rhenium from the columns after the uranium had been eluted with chloride or nitrate solutions. Although the per-chlorate ion was most efficient on a molar basis, nitrate ion combined the benefits of efficiency and low cost. A 3N or stronger concentration of nitrate containing up to 0. 5N H + was found to be the system of choice. A rhenium sulfide concentrate containing up to 14010 Re was obtained from these effluents by hydrogen sulfide precipitation. Preliminary experiments were run to produce rhenium metal powder by oxidation of the concentrate to NH4ReO4 followed by hydrogen reduction at elevated temperature.

Jan 1, 1984

By S. H. Gelles

Samples of poly crystalline zinc of 99.999+ pct purity were observed metallographically after having been exposed to hydrostatic pressures of up to 27 kbars. The deforrnation produced by this treatment was analyzed using X-ray and metallogaphic techniques. Basal-plane slip occurred universally in all grains exumined at the lowest pressure used (8 kbars). At pressures of >23 kbars, {1012} twin nucleation and growth were noted as well as slip. Formation of bend planes, complex kink bands, and recrystallization at the gain boundaries were also observed in this pressure range. These observations are discussed in reference to the expected deformation behavior of zinc under high hydrostatic pressure. It has been shown over the past few years1'3 that anisotropic, poly crystalline metals can be made to deform plastically by the application of a hydrostatic pressure. The effect is greater 1) the larger the anisotropy of linear compressibility and 2) the smaller the stress level needed to produce plastic deformation. Zinc having both very anisotropic linear compressibilities and a very low critical resolved shear stress (CRSS) for basal-plane slip has been shown to exhibit large amounts of plastic deformation when subjected to a hydrostatic pressure.2,3 At pressures up to 15 kbars, grain boundary migration and slip on one set of glide planes have been reported.' After exposing samples to 20 kbars pressure, grain boundary migration, single slip, multiple slip, and twinning have been noted.' The identification of the deformation modes operative under these conditions has not been reported. It was the purpose of this research to identify the deformation modes induced in poly crystal line zinc by the action of a hydrostatic stress and to study the strain accommodation at grain boundaries. Hydrostatic pressure could affect the operational modes of deformation by altering the Peierls-Nabarro stress. This may be roughly approximated by the relationship4

Jan 1, 1967

By Lawrence Adler

The authors are to be complimented on using a novel and potentially helpful technique to analyze the effects of mine roof trusses. However, some criticisms of their application and analysis seem appropriate to further its acceptance. This discussion will deal with the normal structural analysis format covering: 1) material. 2) load, 3) structure, and 4) analysis. It will then briefly review the testing procedures and finally cover miscellaneous items. That the analytical and testing results admittedly disagreed by several orders of magnitude, indicates a need for improved understanding. The introduction of data determined previously was not assisted by references to "Interim" or "Preliminary" reports. This material should have been concisely reformulated for the open discussions that Transactions encourage. In addition, many important simplifying assumptions are tacitly made without recognition, and much less, an attempted justification.

Jan 1, 1979

By Alan Morris

The investigation of the hot-working properties of metals and alloys furnishes a problem which has been attacked in many ways. Tensile, impact and hardness tests on heated specimens have furnished interesting data, but in most cases either the tests are difficult to make or the results hard to translate into terms of practical value. Some investigators have used the drop hammer to advantage. It furnishes a rapid and simple method of comparing the plasticity of metals at elevated temperatures. The indications obtained by its use are of value only in so far as their significance is understood and they can be intelligently used to predict the behavior of a given metal under given hot-working conditions. The work reported here was undertaken not only to add something to the existing volume of such data but also to contribute to our understanding of the results. Doerinckel and Trockels1 used cylindrical specimens and determined the work required to reduce the specimen to one-half the original height. Ellis2 studied the effect of constitution on the malleability of steel at high temperature. His method and that of Kent3 were similar to the one used in the present work. The tests described by Kent were made on samples of tin, zinc, aluminum, copper, lead, 70:30 and 60:40 brasses, with and without a small quantity of lead. He concluded that the test would "indicate whether a material can be forged at a given temperature without cracking." This interpretation must be used with caution. While it is probably true within limits, one must consider the severity of the forging operation. Again, it will not apply strictly to forms of hot working other than forging. For instance, an alloy running 61.0 per cent. copper, 3.25 per cent. lead, remainder zinc, will crack badly in the test, yet, it is extruded commercially. When the possibility of hot-working a new alloy is being considered a study of its drop-hammer test should help

Jan 1, 1931

By Robert H. Aborn, J. J. B. Rutherford

It is now well known that troublesome intercrystalline corrosion may occur in austenitic stainless steels following exposure of the metal to a temperature within the range 1000° to 1500° F. (540° to 815° C.). The present paper describes a satisfactory method of estimating the extent of such corrosion, based on the measurement of the electrical resistance of a specimen before and after attack. This new method enabled us to study quantitatively the effect of several factors upon intergranular corrosion in the 18 Cr, 8 Ni type of alloy. The results show that susceptibility to this attack increases with increasing carbon content and grain size and appears to pass through a maximum for certain combinations of temperature of sensitization and period during which the alloy was maintained at that temperature; and are in complete accord with our interpretation of the mechanism of this phenomenon. The method is probably applicable to other metals or alloys subject to intercrystalline attack, such as the aluminum alloys of the duralumin type. The methods hitherto in use for estimating the degree of intergranular attack fall into three types: (1) microscopic examinationll (2) macroscopic examination of fractures, and (3) determination of the time required for complete failure or disintegration.2 None of these lends itself very well to a measurement of the extent of corrosion. The first two are qualitative in nature and the third provides an arbitrary value largely dependent on individual judgment, since failure is a progressive phenomenon and not a sudden event. Our experience is that weight-loss determinations, although valuable in some types of corrosion investigations, bear no simple relation to intercrystalline corrosion in this type of alloy, as is to be expected since the phenomenon probably involves only the thinnest films between adjacent metallic grains. Measurement of electrical resistance has been used recently in the study of some types of corrosion,3 but seems not to have been applied to

Jan 1, 1932

By Harold B. Goldman, Don Reining

The sand and gravel industry is the largest nonfuel mineral industry in the nation (Drake, 1972), Table 1. In 1970, the production of sand and gravel totaled 944 million tons valued at $1.1 billion. California, which leads the nation with more than 140 million tons, together with Michigan, Ohio, Minnesota, Illinois, Wisconsin, and New York, account for 43 % of the total production in the nation. In commercial usage, "sand" applies to rock or mineral fragments ranging in size from particles retained on a No. 200 sieve (0.074 mm openings) to those passing a No, 4 sieve (4.76 mm openings). "Gravel" consists of rock or mineral fragments larger than 4.76 mm, ranging up to 3%-in. maximum size. The construction industry consumes 96% of the sand and gravel produced; the remainder is sand used for specialized products such as glass (see the chapter on "Silica and Silicon"). Utilization The building industry uses sand and gravel chiefly as aggregate in portland cement concrete, mortar, and plaster; the paving industry uses sand and gravel in both asphaltic mixtures and portland cement concrete. Aggregate is commonly designated as the inert fragmental material which is bound into a conglomerate mass by a cementing material such as portland cement, asphalt, or gypsum plaster.

Jan 1, 1975

By P. A. Beck, A. Merlini

Quantitative texture determinations were made for rolled and for rolled and annealed strips of 3, 6, and 10 pct Zn brasses. The main components of the rolling texture gradually shift over a wide composition range from the orientation characteristic of copper to that of 70-30 brass. At least the main features of the corresponding gradual changes in the annealing texture may be accounted for qualitatively on the basis of the oriented growth theory of annealing textures. All the oriented nucleation-type theories are notably less successful in accounting for the observed textures. EARLIER investigations by von Goeler and Sachs,' Dahl and Pawlek,' and Brick, Martin, and Angier" suggested that the annealing texture of copper is more sensitive to the addition of solute elements than the rolling texture. It was reported3 that the cube texture changes over into a brass-type recrys-tallization texture on addition of about 1 pct Zn, while the deformation texture changes only at about 5 pct Zn. Such behavior would be difficult to reconcile with any theory of annealing texture formation that relates the annealing texture to the deformation texture. In particular, the oriented growth theory of the cube texture" is based on a certain orientation relationship between the cube texture and the main components of the deformation texture which could not be reconciled with the reported behavior of low brasses. It was, therefore, of interest to re-examine these textures by means of the quantitative methods now available. The deformation and annealing textures of rolled a brasses with approximately 3, 6, and 10 pct Zn have been determined in terms of (111) and (200) pole figures. Experimental Methods The chemical analyses of the Cu-Zn alloys of commercial purity used in the present work are given in Table I. Chill-cast bars of the tabulated compositions were rolled and annealed according to the following schedule: I—rolling from 1.2 to 1.02 in. thickness, 15 pct reduction area, annealing 15 min at 450°C; 2— rolling from 1.02 to 0.867 in. thickness, 15 pct reduction area, annealing 15 min at 450°C; 3—rolling from 0.867 to 0.600 in. thickness, 31 pct reduction area, annealing 2 hr at 540°C; 4—rolling from 0.600 to 0.400 in. thickness, 33 pct reduction area, annealing 2 hr at 480°C. In the final straight rolling of 96.25 pct reduction area, the strips were reversed end to end after each pass. The final annealing temperature was determined for each alloy by annealing specimens of the cold-rolled strips in salt bath for 5 min at varying temperatures. The results of the hardness measurements are given in Fig. 1, where the final annealing temperature used for each alloy in determining the annealing texture is indicated by a cross.

Jan 1, 1956

By H. H. Podgurski, J. C. M. Li, Y. T. Chou, F. N. Davis, R. A. Oriani

When an Fe-2 pct A1 alloy is nitrogemted at 500ºC with a gus tnixture (NH3-H2) in which the nitrogen activity has been kept Lou] enough to avoid the formation of iron nitride, a two-phase alloy is generuled which consists of AlN particles and a ferrite phase cotaining a heavy network of dislocations. The amount of nitrogen contained in such an alloy, when equilibrated with the nitrogenating atmosphere, far exceeds both that needed to satisfy the normal solution requirements of a Fe and that needed to convert all of the aluninuwi to AlN. This excess nitrogen is accounted for as being trapped on dislocations, adsorbed at the ferrite -AlN interface, and as an en-Iuznced lattice solubility in strained ferrite. This excessive uptake of nitrogen had previously been attribuled by other investigators to the formation of a nonstoichiornetric aluminum nitride. Isotope exchange experiments revealed various amomts of exchargeable N14 present in the originally nitrided samples that could not be removed by reduction with HS at 500ºC. This exchangeable nitrogen has been identified us that bound to the AlN -ferrite interface. Estimates of inter facial areas in alloys containing -3 pct by weight of A1N are as high as 10 sq m per g of alloy. ThE first1 of this series of papers described the experiments forming the basis for the elucidation of the mechanism of the formation of aluminum nitride particles within an Fe-A1 alloy. It was found that not only are dislocations necessary for the nucleation of the AlN particles but also the nitriding reaction in turn produces a dense network of dislocations in the ferrite matrix. It was also observed that nitrogen in excess of that needed for the formation of stoichiometric AIN is taken up by the alloy without the formation of an iron nitride. The present paper is an analysis of the excess nitrogen sorbed by the nitrided Fe-A1 alloy which considers the structure generated by the formation of the aluminum nitride particles. Because of the high density of dislocations, this system has proved to be quite useful in studying nitrogen-dislocation interactions. Wriedt and Darken2 have already reported such studies in a cold-worked ferritic steel. EXPERIMENTAL Nitrogen Sorption. The specimens of this alloy were cold worked (50 pct reduction) to 0.011 in. thickness and chemically cleaned in a 2:1 concentrated phosphoric acid-50 pct hydrogen peroxide solution before nitrogenation. The flowing nitrogenating atmosphere (11 pct NH3-89 pct H2) was established before the ni- trogenating temperature was reached. The same gravimetric and gas-flow equipment described in an earlier paper1 was also used in this investigation. Changes in nitrogen concentration were followed gravimetrically when establishing the isotherms. In the isotope exchange experiments, concentration changes were followed volumetrically. In some instances chemical analyses (Kjeldahl method) were used to check for material balances in both the gravimetric and volumetric procedures. Our objective was to obtain reversible nitrogen sorption isotherms for alloys equilibrated with NH3-H2 gas mixtures over a large range of nitrogen activity* and temperature. The *Defined as equal to PN H /P3/2 ,where P corresponds to partial pressure in atmospheres. Actually the nitrogen activity, aN, in the alloy equals K PNH3 /p3/2H2, where K is the equilibrium constant for the reaction NH3 = N + 3/2H2. upper limit for nitrogen activity was below that which would produce iron nitride; for reasons which will become apparent later, most of the sorption studies were made in the temperature range between 400" and 500'C. The alloy sample studied most extensively in this investigation was given a series of successive reductions (100 pct H2) and nitrogenating treatments at 500°C to attain a stabilized structure. Presumably some dislocations were lost during these treatments. Throughout most of the sorption studies, temperature was held at ± 1°C and the gas-phase composition was held to k0.2 pet NH3. Based upon the results of numerous diffusion experiments with this alloy* the 'Results to be published in a third paper of this series. times chosen for equilibration were considered more than adequate, Nitrogen Isotope Exchange. The first exchange experiments were carried out by circulating a measured quantity of H2 and NH3* (with a predetermined isotopic *The NH3 was synthesized over a synthetic ammonia iron catalyst using H2, and N2, enriched with N15. AS the NH3 was formed it was removed continuously from the gas phase by circulating the mixture through a refrigerated (78ºK) trap. When most of the nitrogen had been converted to NH3, it was distilled from the trap into a glass storage vessel. composition, N15/N14) over a nitrided specimen at 450°C in a closed glass system. Attempts to reach the exchange limit isothermally, i.e., an isotopic ratio (N15/N14) in the gas phase identical with the extractable nitrogen in the nitrided alloy, were futile. The exchange rate between the gas phase and the alloy was too slow, involving many days. To circumvent the slow exchange with the gas phase, measured amounts of N15 and N14 were introduced into the alloy by nitrogenating with an NH3-H2, mixture at 500°C containing an N15/N14 ratio of 7.76; the charged specimens were then sealed by allowing an oxide film to form over them in air, and in this final condition the specimens were subjected to 500°C in vacuum for various times during which isotope exchange was allowed to proceed within the specimen. It was estab-

Jan 1, 1970

By E. T. Turkdogan

This is a compilation and a critical review of the data on the Fe-Ca-0 ternary system. Using the results on the reductiorz-equilibria, an oxygen potential diagram is drawn for the greater part of the system. A number of univariant systems and invariant points, not determined experimentally, are evaluated by making use of the theorem on univariant curves intersecting at an invariant point. The formation of solid solutions and ternary compounds and the crystal structures of some of the phases in the composition-diagram are given for a feu! temperatures. DURING the past thirty years there has been a continued interest in the study of the Fe-Ca-0 system. A detailed literature survey made by white1 in 1943 indicated that further work was required to clarify the phase relationships; in fact, the work carried out in the subsequent years, reviewed by Burdese2 in 1954, made a valuable contribution to a better understanding of this subject. Most of the data were obtained by the step-wise reduction of mixtures of iron oxides and calcium ferrites. However, there is some uncertainty about the phase relationships in this system, arising mainly from insufficient use of thermodynamic concepts in the construction of phase diagrams. In this paper an attempt is made to establish the invariant points from the available data. OXYGEN POTENTIAL DIAGRAM Schenck and coworkers3,4 were the early investigators who studied part of this system by the step- wise reduction method and suggested the formation of two ternary compounds, CaO.FeO.Fe2O3 and 2Ca0.5Fe0.2Fez03, the latter being referred to as point X. They also deduced from their results that the phases Y (8.74Ca0.32.5Fe0.8.74Fe2O3 and Z (2.02CaO-97.98FeO) were formed near the w?stite corner of the system. Martin and voge15 postulated the existence of the compounds CaO.9FeO and 4Ca0.3Fe3O4; the former is very close to the composition of point Z and the latter to that of CaO.FeO-Fe2O3. The most valuable contribution to the presen knowledge on this system was made by Cirilli and Burdese6-8 who showed by X-ray and chemical anal yses that there were two ternary compounds, CaO-Fe0.Fe2O3 and CaO.3FeO-FezO3; the former is the same as that suggested by Schenck et al. and the latter is close to their point X. The results of Cirilli and Burdese show that the phases Y and Z postulated by Schenk et al. are solid solutions of calcium oxide in w?stite. In most of the above-mentioned reduction-equilibria measurements carbon monoxide-carbon dioxide mixtures were used and in a few cases hydrogen-water vapor mixtures were employed. Using the

Jan 1, 1962

By G. Wakefield, A. H. Daane, D. H. Dennison, F. H. Spedding

Preparation of pure scandium metal was accomplished by calcium reduction of the fluoride by two methods; a low-temperatzdre alloy process and direct reduction with subsequent distillation of the product. The following properties were determined: melting point: 1181OK; boiling point (calculated): 3000°K; lattice constants at 298°K (hexagonal lattice): a = 3.308 * 0.001 A, c = 5.267 * 0.003A; calculated density at 298°K, g per cm3: 2,990 + 0.007; electrical resistivity, ohm-cm: 299°K, 66.6 ± 0.2 x 10 -6; 373oK, 77.4 * 0.2 x 10 -6; thermal coefficient at 299°K, ohm-cm per deg: 5.4 X x; heat of sublimation at 298°K, kcal pel- mole: 80.79. The vapor pressure was determined as a function of temperature between 1505o and 1748°K, with the data fitted to a straight line shielding the equation: Log Pmm = -1.718 X 104/ToK + 8.298. SCANDIUM, element number 21, was first discovered by Nilson in 1879 and was recognized as the Ekaboron as predicted by Mendeleff. As it is in group III of the periodic table, the general properties are a little like aluminum and also resemble quite closely the properties of yttrium and the rare-earth metals, in both the metallic and ionic form. Although the earth's crust contains approximately 5 ppm of scandium (the element is as abundant as arsenic and twice as abundant as boron) it generally occurs so widely distributed that it has earned the reputation of being very rare. The one exception to this is the mineral thortveitite, which has been found in Madagascar (20 pct Sc2O3) and in Norway (35 pct Sc2O3). Scandium also occurs in small but distinct amounts in uranium and rare-earth ores; the recent larger scale processing of these materials has made some scandium available from these sources. As with other naturally-occurring monoisotopic elements (except Be), scandium contains an odd number of protons and an even number of neutrons. Scandium metal was first prepared by Fischer and coworkers1 in 1937 by electrolysis of scandium chloride in a molten eutectic mixture of lithium and potassium chlorides, using molten zinc as a cathode and collector of the scandium metal produced. The zinc was removed from the Zn-2 pct Sc alloy by vacuum distillation, leaving a product reported to be 94 to 98 pct Sc, with the main impurities being iron and silicon. They reported a melting point of 1400° C for this material. Scandium has also been prepared by the reduction of scandium chloride with potassium metal in a glass apparatus by Bommer and Hohmann in 1941,' resulting in a mixture of metal and potassium chloride; these workers did not isolate the metal proper, but the X-ray diffraction of the slag-metal mixture showed it to be hexagonal with a = 3.30A, c = 5.45A. petru3, 4 and coworkers have recently reported the preparation of the metal in a compact form by the reduction of either ScF3 or ScC13 with calcium metal and subsequent distillation of the product. This process probably yielded a metal of high purity, but they list no chemical analysis nor do they list any of the properties of their product. Previous related work in this Laboratory has been concerned with the production of yttrium and the rare-earth metals and the determination of their physical properties. Because of its similarity to these metals, scandium is being included in this study. PREPARATION OF SCANDIUM METAL The preparation of yttrium and the rare-earth metals may be accomplished by reduction of their fluorides with calcium metal in tantalum crucibles.5 This process leads to the introduction of tantalum (up to 0.5 pct) as an impurity in the higher melting rare earths, but since the tantalum occurs as dendrites, uncombined with the rare-earth metals, its presence is not objectionable in some cases. The preparation of scandium metal in this manner, however, was found to yield a product containing 2 to 5 pct Ta. To obtain a purer product, the following two methods were developed for the reduction of scandium fluoride with calcium metal: i) a low-temperature process utilizing zinc to form a low

Jan 1, 1961